Fast-writable and precision-writable high-capacity optical storage media

ABSTRACT

The invention relates to an optical recording medium, comprising a substrate and a recording layer, wherein the recording layer comprises a compound of formula (I), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12  and R 13  are each independently of the others hydrogen, G 1  or C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 7 -C 24 aralkyl, C 6 -C 24 aryl, C 4 -C 12 heteroaryl or C 1 -C 12 heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G 1 , wherein R 1  and R 2 , R 1  and R 13 , R 2  and R 3 , R 3  and R 4 , R 4  and R 5 , R 5  and R 6 , R 6  and R 7 , R 7  and R 8 , R 8  and R 9 , R 9  and R 10 , R 10  and R 11 , R 11  and R 12  and/or R 12  and R 13  can independently of one another be bonded to one another in pairs separately or, when they contain substitutable sites, via a direct bond or via a —CH 2 —, —O—, —S—, —NH— or —NC 1 -C 24 alkyl-bridge in such a manner that, together with the atoms and bonds indicated in formula (I), five- or six-membered, saturated, unsaturated or aromatic, unsubstituted or G 1 -substituted rings are formed, G 1  is any desired substituent,?  x m- is an inorganic, organic organometallic anion, Y n+  is a proton or a metal, ammonium or phosphonium cation, and m and n are each independently of the other a number from 1 to 5, and p and q are each independently of the other O or a number from 0.2 to 6, the ratio of p and q to one another, depending upon m and n and, as applicable, the number of charged G 1 , being such that in formula (I) there is no excess positive or negative charge. Generally the optical recording medium according to the invention additionally comprises a reflecting layer. The recording media according to the invention exhibit high sensitivity and good playback characteristics, especially at high recording and playback speeds. The light stability is also excellent.

The field of the invention is the optical storage of information on write-once storage media, the information pits being differentiated by the different optical properties of a colorant at written and unwritten sites. This technology is usually termed “WORM” (for example “CD-R” or “DVD-R”); those terms have been retained herein.

Compact discs that are writable at a wavelength of from 770 to 830 nm are known from “Optical Data Storage 1989”, Technical Digest Series, Vol. 1, 45 (1989). They are read at a reduced readout power. According to the Orange Book Standard, at the recording wavelength the medium must have a base reflectivity of 65% or more. As recording media it is possible to use, for example, cyanine dyes (JP-58/125246), phthalocyanines (EP-A-676 751, EP-A-712 904), azo dyes (U.S. Pat. No. 5,441,844), double salts (U.S. Pat. No. 4,626,496), dithioethene metal complexes (JP-A-63/288785, JP-A-63/288786), azo metal complexes (U.S. Pat. No. 5,272,047, U.S. Pat. No. 5,294,471, EP-A-649 133, EP-A-649 880) or mixtures thereof (EP-A-649 884).

By using more recent compact high-performance red diode lasers that emit in the range of from 600 to 700 nm it is possible in principle to achieve a 6- to 8-fold improvement in data packing density, in that the track spacing (distance between two turns of the information track) and the size of the pits as well as the redundancy can each be reduced to approximately half the value in comparison with conventional CDs.

This imposes extraordinarily high demands on the recording layer to be used, however, such as high refractive index, high light stability in daylight and under laser radiation of low power density (readout) with, at the same time, high sensitivity under laser radiation of high power density (writing), uniformity of script width at different length pulse durations and also high contrast. The known recording layers still do not possess these properties to an entirely satisfactory extent.

EP-A-0 805 441 describes an optical recording medium comprising xanthene dyes, which can be both recorded and read at from 600 to 700 nm. In the Examples, good results are achieved with a 10 mW laser diode of wavelength 635 nm. It has been found, however, that under practical conditions the results for the dyes disclosed in EP-A-0 805 441 are not able fully to satisfy the demands (which have increased in the interim) in respect of sensitivity, recording speed and mark accuracy and reproducibility, especially in the range from 640 to 680 nm.

U.S. Pat. No. 3,781,711 discloses laser dye compositions comprising dyes having a rigid structure, including 9,9-dimethyl-2-dimethylamino-7H,9H-anthracene-7-dimethyliminium nitrate. Such compounds are used in high dilution.

WO-A-00/64986 describes carbopyronine fluorescent dyes and their use as marker groups in diagnostics. The absorption maxima and the fluorescent yield are not appreciably altered by coupling such compounds to carriers and biomolecules.

The aim of the invention is to provide an optical recording medium, the recording layer of which has high storage capacity combined with excellent other properties. The recording medium should be both writable and readable, with a minimum of errors, at the same wavelength in the range of from 600 to 700 nm (preferably from 630 to 690 nm) at high speed.

Very surprisingly, by the use of certain carbopyronine dyes as recording layer it has been possible to provide an optical recording medium having properties that are astonishingly better than those of recording media known hitherto.

The invention accordingly relates to an optical recording medium comprising a substrate and a recording layer, wherein the recording layer comprises a compound of formula (I)

-   -   wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂ and         R₁₃ are each independently of the others hydrogen, G₁, or         C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, C₃-C₂₄cycloalkyl,         C₃-C₂₄cycloalkenyl, C₇-C₂₄aralkyl, C₆-C₂₄aryl, C₄-C₁₂heteroaryl         or C₁-C₁₂heterocycloalkyl, each unsubstituted or substituted by         one or more identical or different substituents G₁,     -   wherein R₁ and R₂, R₁ and R₁₃, R₂ and R₃, R₃ and R₄, R₄ and R₅,         R₅ and R₆, R₆ and R₇, R₇ and R₈, R₈ and R₉, R₉ and R₁₀, R₁₀ and         R₁₁, R₁₁ and R₁₂ and/or R₁₂ and R₁₃ can independently of one         another be bonded to one another in pairs separately or, when         they contain substitutable sites, via a direct bond or via a         —CH₂—, —O—, —S—, —NH— or —NC₁-C₂₄alkyl-bridge in such a manner         that, together with the atoms and bonds indicated in formula         (I), five- or six-membered, saturated, unsaturated or aromatic,         unsubstituted or G₁-substituted rings are formed,

G₁ is any desired substituent,

X^(m−) is an inorganic, organic or organometallic anion,

Y^(n+) is a proton or a metal, ammonium or phosphonium cation, and

m and n are each independently of the other a number from 1 to 5, and p and q are each independently of the other 0 or a number from 0.2 to 6, the ratio of p and q to one another, depending upon m and n and, as applicable, the number of charged G₁ substituents, being such that in formula (I) there is no excess positive or negative charge.

Generally the optical recording medium according to the invention additionally comprises a reflecting layer, but this is not absolutely necessary per se and it can be omitted depending upon the type of detector.

Each G₁ is, where applicable independently of any other G₁, any desired substituent, for example halogen, —OH, —O⁻, —OA, ═O, —SH, —S⁻, —SA, ═S, —NO₂, —CN, —NH₂, —NHA, —N(A)₂, —N⁺H₃, —N⁺H₂A, —N⁺H(A₂), —N⁺(A)₃, —NHCOA, —N(A)COA, —CHO, —C(A)═O, —CH(OA)₂, —C(A)(OA)₂, —C(OA)₃, —CH═N—A, —C(A)═N—A, —N═CH—A, —N═C(A)₂, —N═N—A, —COO⁻, —COOH, —COOA, —CONH₂, —CONHA, —CON(A)₂, —NHCONH₂, —NHCONHA, —NHCON(A)₂, —N(A)CONH₂, —N(A)CONHA, —N(A)CON(A)₂, —SO₂A, —SO₃ ⁻, —SO₃H, —SO₃A, —PO₃ ⁻, —PO(OA)₂, —Si(A)₃, —OSi(A)₃, —Si(OA)₂(A) or —Si(OA)₃, each A being independently of the others alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aryl or heteroaryl, each of which can be uninterrupted or interrupted by one or more hetero atoms, such as N, O, P and S, for example in the form of a polyalkylene glycol chain, pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, oxybisphenylene or heteroaryl, such as pyridyl, furyl, thienyl or phenothiazinyl.

A is typically C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, C₃-C₂₄cycloalkyl, C₃-C₂₄cycloalkenyl, C₇-C₂₄aralkyl, C₆-C₂₄aryl or C₄-C₁₂heteroaryl.

It will be understood that different As can also be combined, such as, for example, in chromanyl, phosphindolinyl or 1-phenyl-2-pyrazolinyl, that is to say, for example, in substituted form azo-3-methyl-5-oxo-1-phenyl-2-pyrazolin-(4)-yl. It is also possible for alkylene, arylene or aralkylene to be used in place of two As, for example morpholino in place of methyl-3-oxabutyl-amino or 4-methyl-piperidino in place of ethyl-3-azabutyl-amino.

When G₁ contains a radical A, that radical can be unsubstituted or substituted by from 1 to 5 identical or different substituents G₂, each G₂ being as defined for G₁, except that G₂ can only be unsubstituted or mono-substituted by G₃, where G₃ likewise is as defined for G₁, except that G₃ is not further substituted.

Especially the following substituents may be mentioned as G₁: —CH₂—CH₂—OH, —CH₂—O—CH₃, —CH₂—O—(CH₂)₇—CH₃, —CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH(OCH₃)₂, —CH₂—CH₂—CH(OCH₃)₂, —CH₂—C(OCH₃)₂—CH₃, —CH₂—CH₂—O—CH₂—CH₂—O—CH₃, —(CH₂)₃—OH, —(CH₂)₆—OH, —(CH₂)₇—OH, —(CH₂)₈—OH, —(CH₂)₉—OH, —(CH₂)₁₀—OH, —(CH₂)₁₁—OH, —(CH₂)₁₂—OH, —CH₂—Si(CH₃)₃, —CH₂—CH₂—O—Si(CH₃)₂—C(CH₃)₃, —(CH₂)₃—O—Si(CH₃)₂—C(CH₃)₃, —(CH₂)₄—O—Si(C₆H₅)₂—C(CH₃)₃, —(CH₂)₅—O—Si(CH(CH₃)₂)₃, —CH₂—CH₂—CH(CH₃)—CH₂—CH₂—CH(OH)—C(CH₃)₂—OH, —CH₂—CH(CH₃)—CH₂—OH, —CH₂—C(CH₃)₂—CH₂—OH, —CH₂—C(CH₂—OH)₃, —CH₂—CH(OH)—CH₃, —CH₂—CH(OH)—CH₂—OH,

and —(CH₂)₂CH═N—R₁₄, wherein R₁₄ is C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, C₃-C₂₄cycloalkyl, C₃-C₂₄cycloalkenyl, C₇-C₂₄aralkyl, C₆-C₂₄aryl, C₄-C₁₂heteroaryl or C₁-C₁₂heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G₂, or is a metal complex. When R₁₄ is C₁-C₂₄alkyl, it may be uninterrupted or interrupted by from 1 to 3 oxygen and/or silicon atoms. G₂ or G₃ may especially advantageously be alkyl unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical. Such radicals G₁ are of very special importance as R₆.

The compound of formula (I) may optionally also be a dimer of formula

wherein R₁′ to R₁₃′ have the same meanings as R₁ to R₁₃ and an R substituent selected from R₁ to R₁₃ is bonded to an R′ substituent selected from R₁′ to R₁₃′, for example via a direct bond, an alkylene group or a hetero atom, or an R′ substituent selected from R₁′ to R₁₃′ is a direct bond to an R substituent selected from R₁ to R₁₃.

Great importance is attached especially to compounds of formula (II) wherein R₆ is bonded to R₆′, or R₆′ is a direct bond to R₆.

When the numbers p and q are not whole numbers, it is to be understood by formulae (I) and (II) that there is a mixture of a certain molar composition, the individual components of which may also have different stoichiometry.

Alkyl, alkenyl or alkynyl may be straight-chain or branched. Alkenyl is alkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated. Alkynyl is alkyl or alkenyl that is double-unsaturated one or more times, wherein the triple bonds may be isolated or conjugated with one another or with double bonds. Cycloalkyl or cycloalkenyl is monocyclic or polycyclic alkyl or alkenyl, respectively.

C₁-C₂₄Alkyl can therefore be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl or tetracosyl.

C₃-C₂₄Cycloalkyl can therefore be, for example, cyclopropyl, cyclopropyl-methyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl-methyl, trimethyl-cyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, 1-adamantyl, 2-adamantyl, 5α-gonyl or 5ξ-pregnyl.

C₂-C₂₄Alkenyl is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, or any desired isomer of hexenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, heneicosenyl, docosenyl, tetracosenyl, hexadienyl, octadienyl, nonadienyl, decadienyl, dodecadienyl, tetradecadienyl, hexadecadienyl, octadecadienyl or eicosadienyl.

C₃-C₂₄Cycloalkenyl is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl or camphenyl.

C₁-C₂₄Alkoxy is O—C₁-C₂₄alkyl, and C₁-C₂₄alkylthio is S—C₁-C₂₄alkyl.

C₂-C₂₄Alkynyl is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-tetracosyn-24-yl.

C₇-C₂₄Aralkyl is, for example, benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, 9-fluorenyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl or 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl. C₇-C₂₄Aralkyl can also be, for example, 2,4,6-tri-tert-butyl-benzyl or 1-(3,5-dibenzyl-phenyl)-3-methyl-2-propyl. When C₇-C₂₄aralkyl is substituted, either the alkyl moiety or the aryl moiety of the aralkyl group can be substituted, the latter alternative being preferred.

C₆-C₂₄Aryl is, for example, phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or terphenylyl.

Halogen is chlorine, bromine, fluorine or iodine, preferably chlorine or bromine.

C₄-C₁₂Heteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated π-electrons, for example 2-thienyl, 2-furyl, 1-pyrazolyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consisting of thiophene, furan, pyridine, thiazole, oxazole, imidazole, isothiazole, thiadiazole, triazole, pyridine and benzene rings and unsubstituted or substituted by from 1 to 6 ethyl, methyl, ethylene and/or methylene substituents.

Furthermore, aryl and aralkyl can also be aromatic groups bonded to a metal, for example in the form of metallocenes of transition metals known per se, more especially

wherein R₁₅ is CH₂OH, CH₂OA, COOH, COOA and COO⁻.

C₁-C₁₂Heterocycloalkyl is an unsaturated or partially unsaturated ring system radical, for example tetrazolyl; pyrrolidyl, piperidyl, piperazinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, morpholinyl, quinuclidinyl or another C₄-C₁₂heteroaryl that is mono- or poly-hydrogenated.

Y^(n+) as a metal, ammonium or phosphonium cation is, for example, Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Cu²⁺, Ni²⁺, Fe²⁺, Co²⁺, Zn²⁺, Sn²⁺, Cr³⁺, La³⁺, methylammonium, ethylammonium, pentadecylammonium, isopropylammonium, dicyclohexylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltrimethylammonium, benzyltriethylammonium, methyltrioctylammonium, tridodecylmethylammonium, tetrabutylphosphonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyltriphenylphosphonium, or protonated Primen 81R™ or Rosin Amin D™.

X^(m−) as an inorganic, organic or organometallic anion is, for example, the anion of a mineral acid, the conjugate base of an organic acid or an organometal complex anion, for example fluoride, chloride, bromide, iodide, perchlorate, periodate, nitrate, ½ carbonate, hydrogen carbonate, C₁-C₄alkyl sulfate, ½ sulfate, hydrogen sulfate, ⅓ phosphate, ½ hydrogen phosphate, dihydrogen phosphate, ½ C₁-C₄alkanephosphonate, C₁-C₄alkane-C₁-C₁₂alkyl-phosphonate, di-C₁-C₄alkylphosphinate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, acetate, trifluoroacetate, heptafluorobutyrate, ½ oxalate, methanesulfonate, trifluoromethanesulfonate, tosylate, benzenesulfonate, p-chlorobenzenesulfonate, p-nitrobenzenesulfonate, an alcoholate, phenolate (e.g. phenolate itself), carboxylate (also e.g. benzoate), sulfonate or phosphonate) or a negatively charged metal complex.

The person skilled in the art will readily recognise that it is also possible to use other anions with which he is familiar. It will be self-evident to him that $\frac{1}{x}$ of an inorganic, organic or organometallic anion having x negative charges, for example ½.SO₄ ²⁻, is a multiply charged anion which neutralises several singly charged cations or a cation having x charges, as the case may be.

Phenolates or carboxylates are, for example, anions of C₁-C₁₂alkylated, especially tert-C₄-C₈alkylated, phenols or benzoic acids, such as

When X^(m−) is an organometallic anion, it is preferably a metal complex of formula [(L₁)M₁(L₂)]^(m−) (III) or [(L₃)M₂(L₄)]⁻ (IV), wherein M₁ and M₂ are a transition metal, preferably M₁ being Cr³⁺ or Co³⁺ and M₂ being Ni²⁺, Co²⁺ or Cu²⁺, m is a number from 1 to 6, L₁ and L₂ are each independently of the other a ligand of formula

and L₃ and L₄ are each independently of the other a ligand of formula

wherein R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are each independently of the others hydrogen, halogen, cyano, R₂₄, NO₂, NR₂₄R₂₅, NHCO—R₂₄, NHCOOR₂₄, SO₂—R₂₄, SO₂NH₂, SO₂NHR₂₄, SO₂NR₂₄R₂₅, SO₃ ⁻ or SO₃H, preferably hydrogen, chlorine, SO₂NH₂ or SO₂NHR₂₄, and R₂₂ and R₂₃ are each independently of the other CN, CONH₂, CONHR₂₄, CONR₂₄R₂₅, COOR₂₄ or COR₂₄, wherein R₂₄ and R₂₅ are each independently of the other C₁-C₁₂alkyl, C₁-C₁₂alkoxy-C₂-C₁₂alkyl, C₇-C₁₂aralkyl or C₆-C₁₂aryl, preferably C₁-C₄alkyl, each unsubstituted or substituted by hydroxy, halogen, sulfato, C₁-C₆alkoxy, C₁-C₆alkylthio, C₁-C₆alkylamino or by di-C₁-C₆alkylamino, or R₂₄ and R₂₅ together are C₄-C₁₀heterocycloalkyl; it also being possible for R₁₆ and R₁₇, R₁₈ and R₁₉, and/or R₂₀ and R₂₁ to be bonded together in pairs in such a manner that a 5- or 6-membered ring is formed.

Reference is made by way of illustration, but on no account as a limitation, to the individual compounds disclosed in U.S. Pat. No. 5,219,707, U.S. Pat. No. 6,168,843, U.S. Pat. No. 6,242,067, WO-01/19923, WO-01/62853, EP-A-1 125 987, EP-A-1 132 902, JP-A-06/199045, JP-A-07/262604, JP-A-2000/190642 and JP-A-2000/198273.

It is also possible, however, to use any other known transition metal complex anion that contains, for example, a phenolic or phenylcarboxylic azo compound as ligand L₁ or L₂.

Preference is given to compounds of formula (I) wherein R₁, R₄, R₅, R₇, R₈ and R₁₁ are hydrogen; R₂, R₃, R₉, R₁₀, R₁₂ and R₁₃ are each independently of the others methyl, ethyl or R₁₄, it being possible for R₂ and R₃, R₉ and R₁₀, R₁₂ and R₁₃ and/or R₉ and R₁₀ also to be bonded together in pairs via a direct bond, methylene, —O— or —N(C₁-C₄alkyl); and R₆ is hydrogen or C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl, each unsubstituted or mono- to tetra-substituted by halogen, —O⁻, —OR₂₆, —CN, —NR₂₆R₂₇, —N⁺R₂₆R₂₇R₂₈, —N(R₂₆)COR₂₇, —COO⁻, —COOR₂₆, —CONR₂₆R₂₇, R₁₄ or by —N(R₂₆)COR₂₇R₂₈, wherein R₂₆, R₂₇ and R₂₈ are each independently of the others C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl;

all the bridging possibilities, limitations and definitions indicated above otherwise remaining unchanged.

When R₆ is unsubstituted or substituted C₆-C₁₂aryl, it is preferably

wherein R₂₉, R₃₀ and R₃₁ are each independently of the others hydrogen, halogen, COOR₃₂, OR₃₂ or NR₃₂R₃₃, wherein R₃₂ and R₃₃ are each independently of the other hydrogen or C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₁-C₁₂cycloalkyl, C₂-C₁₂cycloalkenyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl, each unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical and uninterrupted or interrupted by 1, 2, 3, 4 or 5 oxygen and/or silicon atoms. R₂₉ is preferably hydrogen, carboxy or COO—C₁-C₈alkyl, R₃₀ is hydrogen or halogen, and R₃₁ is hydrogen, C₁-C₈alkoxy or di-C₁-C₈alkyl-amino.

Special preference is given to compounds of formula (I) wherein R₆ is

or R₃₇, and R₃₄, R₃₅ and R₃₆ are each independently of the others hydrogen or R₃₇.

When R₆ is substituted by R₃₇, then it is preferably substituted by a single R₃₇. The total number of radicals R₃₇ in formula (I) is preferably 0, 1 or 2, especially 0 or 1. The total number of radicals R₃₇ in formula (II) is preferably 0, 1, 2, 3 or 4, especially 0 or 2.

R₃₇ is preferably alkyl uninterrupted or interrupted by from 1 to 3 oxygen and/or silicon atoms and unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical, especially C₁-C₈alkyl, CH₂—CH₂—OH, —CH₂—O—CH₃, —CH₂—O—(CH₂)₇—CH₃, —CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH(OCH₃)₂, —CH₂—CH₂—CH(OCH₃)₂, —CH₂—C(OCH₃)₂—CH₃, —CH₂—CH₂—O—CH₂—CH₂—O—CH₃, —(CH₂)₃—OH, —(CH₂)₆—OH, —(CH₂)₇—OH, —(CH₂)₈—OH, —(CH₂)₉—OH, —(CH₂)₁₀—OH, —(CH₂)₁₁—OH, —(CH₂)₁₂—OH, —CH₂—Si(CH₃)₃, —CH₂—CH₂—O—Si(CH₃)₂—C(CH₃)₃, —(CH₂)₃—O—Si(CH₃)₂—C(CH₃)₃, —(CH₂)₄—O—Si(C₆H₅)₂—C(CH₃)₃, —(CH₂)₅—O—Si(CH(CH₃)₂)₃, —CH₂—CH₂—CH(CH₃)—CH₂—CH₂—CH(OH)—C(CH₃)₂—OH, —CH₂—CH(CH₃)—CH₂—OH, —CH₂—C(CH₃)₂—CH₂—OH, —CH₂—C(CH₂—OH)₃, —CH₂—CH(OH)—CH₃, —CH₂—CH(OH)—CH₂—OH,

C₂-C₈alkylene-O—CO-, C₂-C₈alkylene-COO- or C₂-C₈alkylene-N═CH-, wherein is

Azo metal complex radicals have, for example, the formula —[(L₁)M₁(L₂)]^(m−).

Metallocenyl radicals preferably contain as metal Ni, Co, Cu, Ti or especially Fe. For example, R₃₇ in formula (I) or (II) as a metallocenyl radical may be

[—C₂-C₈alkylene-SO₂]₂-Ø-{hacek over (S)}, [—C₂-C₈alkylene-O—C₂-C₈alkylene-NHSO₂]₂-Ø-{hacek over (S)}, [—C₂-C₈alkylene-NHSO₂]₂-Ø-{hacek over (S)}, [—C₂-C₈alkylene-NH—C₂-C₈alkylene-SO₂]₂-Ø-{hacek over (S)} or [—C₂-C₈alkylene-N(C₁-C₈alkyl)-C₂-C₈alkylene-SO₂]₂-Ø-{hacek over (S)}; or in formula (II) as an azo metal complex radical may be [—C₂-C₈alkylene-SO₂]₂-Ø-, [—C₂-C₈alkylene-NHSO₂]₂-Ø-, [—C₂-C₈alkylene-O—C₂-C₈alkylene-NHSO₂]₂-Ø-, [—C₂-C₈alkylene-NH—C₂-C₈alkylene-SO₂]₂-Ø- or [—C₂-C₈alkylene-N(C₁-C₈alkyl)-C₂-C₈alkylene-SO₂]₂-Ø-, wherein {hacek over (S)} is SO₃-, SO₂-C₁-C₈alkyl, SO₂NR₃₉R₄₀, R₃₉ and R₄₀ are each independently of the other hydrogen or C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₁-C₁₂cycloalkyl, C₂-C₁₂cycloalkenyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl, each uninterrupted or interrupted by from 1 to 5 oxygen and/or silicon atoms and unsubstituted or substituted by one or two hydroxy substituents, and Ø is the bivalent radical of an organometallic anion selected from the group consisting of

and those of the formulae Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, Q15, Q16, Q17, Q18, Q19, Q20, Q21, Q22, Q23, Q24 and Q25 given hereinbelow. -Alkylene-SO₂-Ø, -alkylene-NHSO₂-Ø, -alkylene-O-alkylene-NHSO₂-Ø, -alkylene-NH-alkylene-SO₂-Ø or -alkylene-N(alkyl)-alkylene-SO₂-Ø are preferably —(CH₂)₂—SO₂-Ø, —(CH₂)₂—NHSO₂-Ø, —(CH₂)₂—O—(CH₂)₂—NHSO₂-Ø, —(CH₂)₂—NH—(CH₂)₂—SO₂-Ø, —(CH₂)₆—NHSO₂-Ø or —(CH₂)₂—N(C₄H₉)—(CH₂)₂—SO₂-Ø.

Of special interest are compounds of formula (I) substituted by azo metal complex radicals such as, for example,

and also compounds of formula (II) wherein two radicals of formula (I) are linked via a bridge of formula

Those preferences apply to each of the sub-structures contained in formula (I) or (II), in each case independently of any other sub-structures which may be present, provided that the condition inherent in formula (I) or (II) is fulfilled, i.e. that the resulting compound does not have an excess positive or negative charge. Sub-structures of formula (I) or (II) are to be understood as including their three components carbopyronine, (X^(m−))_(p) and (Y^(n+))_(q) that are not bonded to one another.

Special preference is given also to compounds of formula (I) or (II) wherein Y^(n+) is [NH₂R₃₈R₃₉]⁺, R₃₈ being hydrogen or C₁-C₁₂alkyl and R₃₉ being C₁-C₂₄alkyl or C₇-C₂₄aralkyl, and R₃₈ and R₃₉ together having from 8 to 25 carbon atoms.

Special preference is given also to compounds of formula (I) or (II) wherein m and n are each the number 1, p is a number from 1 to 2½, and q is a number from 0 to 1½, the sum of positive charges in formula (I) or (II) being equal to the sum of negative charges.

Very special preference is given to the compounds of formula [G⁺]₁-[Q⁻]₁ (V) or [G⁺]₁(F)_(r)(Cl)_(s)-[Q⁻]₁ (VI), wherein G⁺ is a cation selected from the group consisting of

and tautomers thereof, r is a number from 1 to 6, s is a number from 1 to 4, and Q⁻ is an organometallic anion selected from the group consisting of

In formula (VI), preferably r is 0 and s is 1 or 2, or especially r is 1 and s is 0, for example compounds wherein G⁺ is

The compounds of formulae (I) and (II) are in some cases known compounds which can be found, for example, in the prior art mentioned above. Some of them are new, but they can be prepared analogously to the known compounds by methods known per se, for example by methods disclosed in J. Chem. Soc. III 1963/2655-2662, J. Chem. Soc. (B) 1967/91-92, J. Chem. Soc. (B) 1969/1068-1071, J. Chem. Soc. (B) 1971/319-324, J. Chem. Soc. (B) 1971/1468-1471 or Heterocycles 21/1, 167-190 [1984]. The compounds used according to the invention can also be prepared from their leuco forms, some of which are known for photographic and electrophotographic applications, according to methods known to the person skilled in the art. Metal complexes, preferably those of formula (III), are well known from the specialist literature. In particular, they may be those metal complexes described in GB 1 599 812 or EP 450 421, and reference is made expressly to the teaching contained therein.

Compounds of formula (I) or their precursors are preferably prepared by oxidation of a compound of formula

it having been found, most surprisingly, that liquid acids, for example acetic acid, are especially advantageous solvents and (meta)periodate is an especially advantageous oxidising agent, especially in combination. The reaction proceeds more selectively and the compounds in question are obtained in better yield and better purity, which results in better application-related properties in optical storage media. Ammonium (meta)periodates, especially tetrabutylammonium (meta)periodate, and acetic acid, especially glacial acetic acid, are particularly advantageous.

The invention accordingly relates also to a process for the preparation of a compound of formula (I), wherein a compound of structure

is oxidised in the presence of a C₁-C₁₈carboxylic acid. The amount of C₁-C₁₈carboxylic acid is advantageously from 0.1 to 10 000 parts by weight, based on (X).

The carbopyronine dyes used according to the invention have in ethanolic solution a narrow absorption band having its maximum at from 540 to 640 nm. Very surprisingly, they also have a comparatively weak tendency towards agglomeration in the solid state, so that the absorption curve remains advantageously narrow also in the solid state. This is true especially in the presence of metal-containing anions (X^(m−))_(p), for example the metal complex anions indicated above.

The carbopyronine dyes used according to the invention also have, in the form of a solid film, as used in optical storage media, at the longer wavelength flank of the absorption band a high refractive index which preferably achieves a peak value of from 2.0 to 3.0 in the range of from 600 to 700 nm, so that a medium having high reflectivity as well as high sensitivity and good playback characteristics in the desired spectral range is achieved.

The substrate, which functions as support for the layers applied thereto, is advantageously semi-transparent (T≧10%) or preferably transparent (T≧90%). The support can have a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm.

The recording layer is preferably arranged between the transparent substrate and the reflecting layer. The thickness of the recording layer is from 10 to 1000 nm, preferably from 30 to 300 nm, especially about 80 nm, for example from 60 to 120 nm. The absorption of the recording layer is typically from 0.1 to 1.0 at the absorption maximum. The layer thickness is very especially chosen in known manner depending upon the respective refractive indices in the non-written state and in the written state at the reading wavelength, so that in the non-written state constructive interference is obtained, but in the written state destructive interference is obtained, or vice versa.

The reflecting layer, the thickness of which can be from 10 to 150 nm, preferably has high reflectivity (R≧45%, especially R≧60%), coupled with low transparency (T≦10%). In further embodiments, for example in the case of media having a plurality of recording layers, the reflector layer may likewise be semi-transparent, that is to say may have comparatively high transparency (for example T≧50%) and low reflectivity (for example R≦30%).

The uppermost layer, for example the reflective layer or the recording layer, depending upon the layer structure, is advantageously additionally provided with a protective layer having a thickness of from 0.1 to 1000 μm, preferably from 0.1 to 50 μm, especially from 0.5 to 15 μm. Such a protective layer can, if desired, serve also as adhesion promoter for a second substrate layer applied thereto, which is preferably from 0.1 to 5 mm thick and consists of the same material as the support substrate.

The reflectivity of the entire recording medium is preferably at least 15%, especially at least 40%.

The main features of the recording layer according to the invention are the very high initial reflectivity in the said wavelength range of the laser diodes, which can be modified with especially high sensitivity; the high refractive index; the narrow absorption band in the solid state; the good uniformity of the script width at different pulse durations; the good light stability; and the good solubility in polar solvents.

The recording medium according to the invention is neither writable nor readable using the infra-red laser diodes of customary CD apparatus in accordance with the requirements of the Orange Book Standard, because at 780 nm the refractive indices (n) characteristically lie between 1.4 and 1.9 and their imaginary components (k) between 0 and a maximum of 0.04. As a result, the risk of damage in the event of an erroneous attempt at writing using an apparatus not capable of high resolution is largely averted, which is of advantage. The use of dyes of formula (I) results in advantageously homogeneous, amorphous and low-scatter recording layers having a high refractive index, and the absorption edge is surprisingly especially steep even in the solid phase. Further advantages are high light stability in daylight and under laser radiation of low power density with, at the same time, high sensitivity under laser radiation of high power density, uniform script width, high contrast, and also good thermal stability and storage stability.

At a relatively high recording speed, the results obtained are surprisingly better than with previously known recording media. The marks are more precisely defined relative to the surrounding medium, and thermally induced deformations do not occur. The error rate (BLER) and the statistical variations in mark length (jitter) are also low both at normal recording speed and at relatively high recording speed, so that an error-free recording and playback can be achieved over a large speed range. There are virtually no rejects even at high recording speed, and the reading of written media is not slowed down by the correction of errors. The advantages are obtained in the entire range of from 600 to 700 nm (preferably from 630 to 690 nm), but are especially marked at from 640 to 680 nm, more especially from 650 to 670 nm, particularly at 658±5 nm.

Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics. Preferred supports are glass and homo- or co-polymeric plastics. Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins. The substrate can be in pure form or may also comprise customary additives, for example UV absorbers or dyes, as proposed e.g. in JP 04/167 239 as light-stabilisers for the recording layer. In the latter case it may be advantageous for the dye added to the support substrate to have an absorption maximum hypsochromically shifted relative to the dye of the recording layer by at least 10 nm, preferably by at least 20 nm.

The substrate is advantageously transparent over at least a portion of the range from 600 to 700 nm (preferably as indicated above), so that it is permeable to at least 90% of the incident light of the writing or readout wavelength. The substrate has preferably on the coating side a spiral guide groove having a groove depth of from 50 to 500 nm, a groove width of from 0.2 to 0.8 μm and a track spacing between two turns of from 0.4 to 1.6 μm, especially having a groove depth of from 100 to 200 nm, a groove width of 0.3 μm and a spacing between two turns of from 0.6 to 0.8 μm. The storage media according to the invention are therefore suitable especially advantageously for the optical recording of DVD media having the currently customary pit width of 0.4 μm and track spacing of 0.74 μm. The increased recording speed relative to known media allows synchronous recording or, for special effects, even accelerated recording of video sequences with excellent image quality.

The recording layer, instead of comprising a single compound of formula (I) or (II), may also comprise a mixture of such compounds having, for example, 2, 3, 4 or 5 carbopyronine dyes according to the invention. By the use of mixtures, for example mixtures of isomers or homologues as well as mixtures of different structures, the solubility can often be increased and/or the amorphous content improved. If desired, mixtures of ion pair compounds may have different anions, different cations or both different anions and different cations.

For a further increase in stability it is also possible, if desired, to add known stabilisers in customary amounts, for example a nickel dithiolate described in JP 04/025 493 as light stabiliser.

The recording layer comprises a compound of formula (I) or (II) or a mixture of such compounds advantageously in an amount sufficient to have a substantial influence on the refractive index, for example at least 30% by weight, preferably at least 60% by weight, especially at least 80% by weight. The recording layer can especially valuably comprise a compound of formula (I) or a mixture of a plurality of such compounds as main component, or may consist exclusively or substantially of one or more compounds of formula (I).

Further customary constituents are possible, for example other chromophores (for example those disclosed in WO-01/75873, or others having an absorption maximum at from 300 to 1000 nm), stabilisers, ¹O₂—, triplet- or luminescence-quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical recording media. Preferably, stabilisers or fluoresence-quenchers are added if desired.

When the recording layer comprises further chromophores, they may in principle be any dye that can be decomposed or modified by the laser radiation during the recording, or they may be inert towards the laser radiation. When the further chromophores are decomposed or modified by the laser radiation, this can take place directly by absorption of the laser radiation or can be induced indirectly by the decomposition of the compounds of formula (I) or (II) according to the invention, for example thermally.

Naturally, further chromophores or coloured stabilisers may influence the optical properties of the recording layer. It is therefore preferable to use further chromophores or coloured stabilisers, the optical properties of which conform as far as possible to those of the compounds formula (I) or (II) or are as different as possible, or the amount of further chromophores is kept small.

When further chromophores having optical properties that conform as far as possible to those of compounds formula (I) or (II) are used, preferably this should be the case in the range of the longest-wavelength absorption flank. Preferably the wavelengths of the inversion points of the further chromophores and of the compounds of formula (I) or (II) are a maximum of 20 nm, especially a maximum of 10 nm, apart. In that case the further chromophores and the compounds of formula (I) or (II) should exhibit similar behaviour in respect of the laser radiation, so that it is possible to use as further chromophores known recording agents the action of which is synergistically enhanced or heightened by the compounds of formula (I) or (II).

When further chromophores or coloured stabilisers having optical properties that are as different as possible from those of compounds of formula (I) or (II) are used, they advantageously have an absorption maximum that is hypsochromically or bathochromically shifted relative to the dye of formula (I) or (II). In that case the absorption maxima are preferably at least 50 nm, especially at least 100 nm, apart. Examples thereof are UV absorbers that are hypsochromic to the dye of formula (I) or (II), or coloured stabilisers that are bathochromic to the dye of formula (I) or (II) and have absorption maxima lying, for example, in the NIR or IR range. Other dyes can also be added for the purpose of colour-coded identification, colour-masking (“diamond dyes”) or enhancing the aesthetic appearance of the recording layer. In all those cases, the further chromophores or coloured stabilisers should preferably exhibit behaviour towards light and laser radiation that is as inert as possible.

When another dye is added in order to modify the optical properties of the compounds of formula (I) or (II), the amount thereof is dependent upon the optical properties to be achieved. The person skilled in the art will find little difficulty in varying the ratio of additional dye to compound of formula (I) or (II) until he obtains his desired result.

When chromophores or coloured stabilisers are used for other purposes, the amount thereof should preferably be small so that their contribution to the total absorption of the recording layer in the range of from 600 to 700 nm is a a maximum of 20%, preferably a maximum of 10%. In such a case, the amount of additional dye or stabiliser is advantageously a maximum of 50% by weight, preferably a maximum of 10% by weight, based on the recording layer.

Most preferably, however, no additional chromophore is added, unless it is a coloured stabiliser.

Further chromophores that can be used in the recording layer in addition to the compounds of formula (I) or (II) are, for example, cyanines and cyanine metal complexes (U.S. Pat. No. 5,958,650), styryl compounds (U.S. Pat. No. 6,103,331), oxonol dyes (EP-A-833 314), azo dyes and azo metal complexes (JP-A-11/028865), phthalocyanines (EP-A-232 427, EP-A-337 209, EP-A-373 643, EP-A-463 550, EP-A-492 508, EP-A-509 423, EP-A-511 590, EP-A-513 370, EP-A-514 799, EP-A-518 213, EP-A-519 419, EP-A-519 423, EP-A-575 816, EP-A-600 427, EP-A-676 751, EP-A-712 904, WO-98/14520, WO-00/09522, PCT/EP-02/03945), porphyrins and azaporphyrins (EP-A-822 546, U.S. Pat. No. 5,998,093), dipyrromethene dyes and metal chelate compounds thereof (EP-A-822 544, EP-A-903 733), xanthene dyes and metal complex salts thereof (U.S. Pat. No. 5,851,621) or quadratic acid compounds (EP-A-568 877), or oxazines, dioxazines, diazastyryls, formazans, anthraquinones or phenothiazines; this list is on no account exhaustive and the person skilled in the art will interpret the list as including further known dyes.

Stabilisers, ¹O₂—, triplet- or luminescence-quenchers are, for example, metal complexes of N- or S-containing enolates, phenolates, bisphenolates, thiolates or bisthiolates or of azo, azomethine or formazan dyes, such as bis(4-dimethyl-aminodithiobenzil)nickel [CAS No 38465-55-3], ®Irgalan Bordeaux EL, ®Cibafast N or similar compounds, hindered phenols and derivatives thereof (optionally also as counter-ions X), such as ®Cibafast AO, o-hydroxyphenyl-triazoles or -triazines or other UV absorbers, such as ®Cibafast W or ®Cibafast P or hindered amines (TEMPO or HALS, also as nitroxides or NOR-HALS, optionally also as counter-ions X), and also as cations diimmonium, Paraquat™ or Orthoquat™ salts, such as ®Kayasorb IRG 022, ®Kayasorb IRG 040, optionally also as radical ions, such as N,N,N′,N′-tetrakis(4-dibutylaminophenyl)-p-phenylene-amine-ammonium hexafluorophosphate, hexafluoroantimonate or perchlorate. The latter are available from Organica (Wolfen/DE); ®Kayasorb brands are available from Nippon Kayaku Co. Ltd., and ®Irgalan and ®Cibafast brands are available from Ciba Spezialitätenchemie AG.

Many such structures are known, some of them also in connection with optical recording media, for example from U.S. Pat. No. 5,219,707, JP-A-06/199045, JP-A-07/76169, JP-A-07/262604 or JP-A-2000/272241. They may be, for example, salts of the metal complex anions disclosed above with any desired cations, for example the cations disclosed above.

Also suitable are neutral metal complexes, for example those metal complexes disclosed in EP 0 822 544, EP 0 844 243, EP 0 903 733, EP 0 996 123, EP 1 056 078, EP 1 130 584 or U.S. Pat. No. 6,162,520, for example

and also those of the formula (L₃)M₂(L₅) (VII), (L₆)M₂(L₇) (VIII) or M₂(L₈) (IX), wherein L₅ is C₁-C₁₂alkyl-OH, C₆-C₁₂aryl-OH, C₇-C₁₂aralkyl-OH, C₁-C₁₂alkyl-SH, C₆-C₁₂aryl-SH, C₇-C₁₂aralkyl-SH, C₁-C₁₂alkyl-NH₂, C₆-C₁₂aryl-NH₂, C₇-C₁₂aralkyl-NH₂, di-C₁-C₁₂alkyl-NH, di-C₆-C₁₂aryl-NH, di-C₇-C₁₂aralkyl-NH, tri-C₁-C₁₂alkyl-N, tri-C₆-C₁₂aryl-N or tri-C₇-C₁₂aralkyl-N,

M₂ and R₁₆ to R₂₁ being as defined above.

A particular example of an additive of formula (IX) that may be mentioned is a copper complex, illustrated e.g. by a compound of formula

A particular example of an additive of formula (VII) that may be mentioned is a nickel bisphenolate, illustrated e.g. by the compound of formula

The person skilled in the art will know from other optical information media, or will easily identify, which additives in which concentration are best suited to which purpose. Suitable concentrations of additives are, for example, from 0.001 to 1000% by weight, preferably from 1 to 50% by weight, based on the recording medium of formula (I) or (II).

The recording medium according to the invention, in addition to comprising compounds of formula (I) or (II), may additionally comprise salts, for example ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium sulfate, sodium methyl sulfonate or sodium methyl sulfate, the ions of which may originate e.g. from the components used. The additional salts, if present, may be present preferably in amounts of up to 20% by weight, based on the total weight of the recording layer.

Reflecting materials suitable for the reflective layer include especially metals, which provide good reflection of the laser radiation used for recording and playback, for example the metals of Main Groups III, IV and V and of the Sub-Groups of the Periodic Table of the Elements. Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and alloys thereof are especially suitable. Special preference is given to a reflective layer of aluminium, silver, copper, gold or an alloy thereof, on account of their high reflectivity and ease of production.

Materials suitable for the protective layer include chiefly plastics, which are applied in a thin layer to the support or the uppermost layer either directly or with the aid of adhesive layers. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which may be modified further, for example written. The plastics may be thermosetting plastics and thermoplastic plastics. Preference is given to radiation-cured (e.g using UV radiation) protective layers, which are particularly simple and economical to produce. A wide variety of radiation-curable materials are known. Examples of radiation-curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having C₁-C₄alkyl groups in at least two ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl groups, e.g. dimethylmaleinimidyl groups.

The recording media according to the invention may also have additional layers, for example interference layers. It is also possible to construct recording media having a plurality of (for example two) recording layers. The structure and the use of such materials are known to the person skilled in the art. Preferred, if present, are interference layers that are arranged between the recording layer and the reflecting layer and/or between the recording layer and the substrate and consist of a dielectric material, for example as described in EP 353 393 of TiO₂, Si₃N₄, ZnS or silicone resins.

The recording media according to the invention can be produced by processes known per se, various methods of coating being employable depending upon the materials used and their function.

Suitable coating methods are, for example, immersion, pouring, brush-coating, blade-application and spin-coating, as well as vapour-deposition methods carried out under a high vacuum. When pouring methods are used, for example, solutions in organic solvents are generally used. When solvents are employed, care should be taken that the supports used are insensitive to those solvents. Suitable coating methods and solvents are described, for example, in EP-A-401 791.

The recording layer is preferably applied by spin-coating with a dye solution, solvents that have proved satisfactory being especially alcohols, e.g. 2-methoxyethanol, n-propanol, isopropanol, isobutanol, n-butanol, amyl alcohol or 3-methyl-1-butanol or preferably fluorinated alcohols, e.g. 2,2,2-trifluoro-ethanol or 2,2,3,3-tetrafluoro-1-propanol, and mixtures thereof. It will be understood that other solvents or solvent mixtures can also be used, for example those solvent mixtures described in EP-A-511 598 and EP-A-833 316. Ethers (dibutyl ether), ketones (2,6-dimethyl-4-heptanone, 5-methyl-2-hexanone) or saturated or unsaturated hydrocarbons (toluene, xylene) can also be used, for example in the form of mixtures (e.g. dibutyl ether/2,6-dimethyl-4-heptanone) or mixed components.

The person skilled in the art of spin-coating will in general routinely try out all the solvents with which is he is familiar, as well as binary and ternary mixtures thereof, in order to discover the solvents or solvent mixtures which result in a high-quality and, at the same time, cost-effective recording layer containing the solid components of his choice. Known methods of process engineering can also be employed in such optimisation procedures, so that the number of experiments to be carried out can be kept to a minimum.

The invention therefore relates also to a method of producing an optical recording medium, wherein a solution of a compound of formula (I) in an organic solvent is applied to a substrate having pits. The application is preferably carried out by spin-coating.

The application of the metallic reflective layer is preferably effected by sputtering, vapour-deposition in vacuo or by chemical vapour deposition (CVD). The sputtering technique is especially preferred for the application of the metallic reflective layer on account of the high degree of adhesion to the support. Such techniques are known and are described in specialist literature (e.g. J. L. Vossen and W. Kern, “Thin Film Processes”, Academic Press, 1978).

The structure of the recording medium according to the invention is governed primarily by the readout method; known function principles include the measurement of the change in the transmission or, preferably, in the reflection, but it is also known to measure, for example, the fluorescence instead of the transmission or reflection.

When the recording material is structured for a change in reflection, the following structures, for example, can be used: transparent support/recording layer (optionally multilayered)/reflective layer and, if expedient, protective layer (not necessarily transparent); or support (not necessarily transparent)/reflective layer/recording layer and, if expedient, transparent protective layer. In the first case, the light is incident from the support side, whereas in the latter case the radiation is incident from the recording layer side or, where applicable, from the protective layer side. In both cases the light detector is located on the same side as the light source. The first-mentioned structure of the recording material to be used according to the invention is generally preferred.

When the recording material is structured for a change in light transmission, the following different structure, for example, comes into consideration: transparent support/recording layer (optionally multilayered) and, if expedient, transparent protective layer. The light for recording and for readout can be incident either from the support side or from the recording layer side or, where applicable, from the protective layer side, the light detector in this case always being located on the opposite side.

Suitable lasers are those having a wavelength of 600-700 nm, for example commercially available lasers having a wavelength of 602, 612, 633, 635, 647, 650, 670 or 680 nm, especially semi-conductor lasers, such as GaAsAl, InGaAlP or GaAs laser diodes having a wavelength especially of about 635, 650 or 658 nm. The recording is effected, for example, point for point in a manner known per se, by modulating the laser in accordance with the mark lengths and focussing its radiation onto the recording layer. It is known from the specialist literature that other methods are currently being developed which may also be suitable for use.

The process according to the invention allows the storage of information with great reliability and stability, distinguished by very good mechanical and thermal stability and by high light stability and by sharp boundary zones of the pits. Special advantages include the high contrast, the low jitter and the surprisingly high signal/noise ratio, so that excellent readout is achieved. The high storage capacity is especially valuable in the field of video.

The readout of information is carried out according to methods known per se by registering the change in absorption or reflection using laser radiation, for example as described in “CD-Player und R-DAT Recorder” (Claus Biaesch-Wiepke, Vogel Buchverlag, Würzburg 1992).

The information-containing medium according to the invention is especially an optical information material of the WORM type. It may be used, for example, as a playable DVD (digital versatile disk), as storage material for a computer or as an identification and security card or for the production of diffractive optical elements, for example holograms.

The invention accordingly relates also to a method for the optical recording, storage and playback of information; wherein a recording medium according to the invention is used. The recording and the playback advantageously take place in a wavelength range of from 600 to 700 nm.

The following Examples illustrate the invention in greater detail:

EXAMPLE 1

98.22 g of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenyl-idene]-N-methyl-perchlorate are dissolved in 25 liters of ethanol. Separately, 256.25 g of the sodium salt of the metal complex of formula Q20 (in each case based on dry weight) are then dissolved in 40 liters of ethanol, with heating to 65° C. After cooling to 23° C., the two solutions are combined (for example by pumping the second solution into the first), stirred for 30 minutes to complete the reaction and clarified by filtration. The solution is concentrated by evaporation under a low vacuum using a rotary evaporator with a water bath at a temperature of about 65° C., yielding 353.63 g of crude product. 15 liters of water are added to the crude product and the mixture is treated mechanically and/or by ultrasound for 30 minutes at 10-20° C. in order to dissolve the inorganic salts. After filtration and washing with 10 liters of water, the filtration residue is dried at 80° C./1.6·10³ Pa, yielding 322.30 g of the product of formula

EXAMPLE 2

The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula

EXAMPLE 3

The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula

EXAMPLE 4

The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula

EXAMPLE 5

The procedure is as in Example 1, but instead of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is used an equimolar amount of the product of formula

EXAMPLE 6

The procedure is as in Example 1, but instead of the metal complex of formula Q20 there is used an equimolar amount of the metal complex of formula Q3.

EXAMPLE 7

2% by weight of the product according to Example 1 are dissolved in 2,2,3,3-tetrafluoro-1-propanol and the solution is filtered through a Teflon filter of pore size 0.2 μm and applied by spin-coating at 1000 rev/min to the surface of a 0.6 mm thick, grooved polycarbonate disc (groove depth: 170 nm, groove width: 350 nm, track spacing: 0.74 μm) of 120 mm diameter. The excess solution is spun off by increasing the rotational speed. On evaporation of the solvent, the dye remains behind in the form of a uniform, amorphous solid layer. After drying in a circulating-air oven at 70° C. (10 min), the solid layer exhibits an absorption of 0.45 at 625 nm. In a vacuum coating apparatus (Twister™, Balzers Unaxis), a 60 nm thick silver layer is then applied to the recording layer by atomisation. Then a 6 μm thick protective layer of a UV-curable photopolymer (650-020, DSM) is applied thereto by means of spin-coating. The recording support exhibits a reflectivity of 47% at 658 nm. The optical constants (absorption maximum λ_(max), refractive index at 658 nm n₆₅₈, absorption coefficient at 658 nm k₆₅₈) are determined reflectometrically (ETA-RT™, ETA-Optik Steag-Hamatech): λ_(max)=624 nm; n₆₅₈=2.29; k₆₅₈=0.21.

Using a commercial test apparatus (DVDT-R 650™, Expert Magnetics), marks are written into the active layer at a speed of 3.5 m/sec using a laser diode of wavelength 658 nm and laser power of 9.2 mW. Then, using the same test apparatus, the dynamic parameters are determined, there being obtained good measured values:

-   -   DTC Jitter=8.8%; R14H=47%; |14/|14H=0.72.

EXAMPLE 8

The procedure is as in Example 7, but the product according to Example 6 is used instead of the product according to Example 1. The optical constants are determined reflectometrically as in Example 7:

-   -   λ_(max)=626 nm; n₆₅₈=2.55; k₆₅₈=0.33.

COMPARISON EXAMPLE 9

The procedure is as in Examples 7 and 8, but the product according to Example A8 of EP-A-0 805 441 is used instead of the products according to Examples 1 and 6. The optical constants are determined reflectometrically in the same way:

-   -   λ_(max)=581 nm; n₆₅₈=1.94; k₆₅₈=0.016.

This disc cannot be written using commercial recording apparatus (Pioneer A03 DVD-R(G)) on account of insufficient sensitivity.

EXAMPLES 10-2094

The procedure is as in Examples 7-9, but the following compounds of formula [G⁺].[X⁻], which can be prepared analogously to Examples 1-6, are used:

Ex. [G⁺] [X⁻] 10 G1 Q2 11 G2 Q2 12 G3 Q2 13 G4 Q2 14 G5 Q2 15 G6 Q2 16 G7 Q2 17 G8 Q2 18 G9 Q2 19 G10 Q2 20 G11 Q2 21 G12 Q2 22 G13 Q2 23 G14 Q2 24 G15 Q2 25 G16 Q2 26 G17 Q2 27 G18 Q2 28 G19 Q2 29 G20 Q2 30 G21 Q2 31 G22 Q2 32 G23 Q2 33 G24 Q2 34 G25 Q2 35 G26 Q2 36 G27 Q2 37 G28 Q2 38 G29 Q2 39 G30 Q2 40 G31 Q2 41 G32 Q2 42 G33 Q2 43 G34 Q2 44 G35 Q2 45 G36 Q2 46 G37 Q2 47 G38 Q2 48 G39 Q2 49 G40 Q2 50 G41 Q2 51 G42 Q2 52 G43 Q2 53 G44 Q2 54 G45 Q2 55 G46 Q2 56 G47 Q2 57 G48 Q2 58 G49 Q2 59 G50 Q2 60 G51 Q2 61 G52 Q2 62 G53 Q2 63 G54 Q2 64 G55 Q2 65 G56 Q2 66 G57 Q2 67 G58 Q2 68 G59 Q2 69 G60 Q2 70 G61 Q2 71 G62 Q2 72 G63 Q2 73 G64 Q2 74 G65 Q2 75 G66 Q2 76 G67 Q2 77 G68 Q2 78 G69 Q2 79 G70 Q2 80 G71 Q2 81 G72 Q2 82 G73 Q2 83 G74 Q2 84 G75 Q2 85 G76 Q2 86 G77 Q2 87 G78 Q2 88 G79 Q2 89 G80 Q2 90 G81 Q2 91 G82 Q2 92 G83 Q2 93 G84 Q2 94 G85 Q2 95 G86 Q2 96 G87 Q2 97 G2 Q3 98 G3 Q3 99 G4 Q3 100 G5 Q3 101 G6 Q3 102 G7 Q3 103 G8 Q3 104 G9 Q3 105 G10 Q3 106 G11 Q3 107 G12 Q3 108 G13 Q3 109 G14 Q3 110 G15 Q3 111 G16 Q3 112 G17 Q3 113 G18 Q3 114 G19 Q3 115 G20 Q3 116 G21 Q3 117 G22 Q3 118 G23 Q3 119 G24 Q3 120 G25 Q3 121 G26 Q3 122 G27 Q3 123 G28 Q3 124 G29 Q3 125 G30 Q3 126 G31 Q3 127 G32 Q3 128 G33 Q3 129 G34 Q3 130 G35 Q3 131 G36 Q3 132 G37 Q3 133 G38 Q3 134 G39 Q3 135 G40 Q3 136 G41 Q3 137 G42 Q3 138 G43 Q3 139 G44 Q3 140 G45 Q3 141 G46 Q3 142 G47 Q3 143 G48 Q3 144 G49 Q3 145 G50 Q3 146 G51 Q3 147 G52 Q3 148 G53 Q3 149 G54 Q3 150 G55 Q3 151 G56 Q3 152 G57 Q3 153 G58 Q3 154 G59 Q3 155 G60 Q3 156 G61 Q3 157 G62 Q3 158 G63 Q3 159 G64 Q3 160 G65 Q3 161 G66 Q3 162 G67 Q3 163 G68 Q3 164 G69 Q3 165 G70 Q3 166 G71 Q3 167 G72 Q3 168 G73 Q3 169 G74 Q3 170 G75 Q3 171 G76 Q3 172 G77 Q3 173 G78 Q3 174 G79 Q3 175 G80 Q3 176 G81 Q3 177 G82 Q3 178 G83 Q3 179 G84 Q3 180 G85 Q3 181 G86 Q3 182 G87 Q3 183 G1 Q4 184 G2 Q4 185 G3 Q4 186 G4 Q4 187 G5 Q4 188 G6 Q4 189 G7 Q4 190 G8 Q4 191 G9 Q4 192 G10 Q4 193 G11 Q4 194 G12 Q4 195 G13 Q4 196 G14 Q4 197 G15 Q4 198 G16 Q4 199 G17 Q4 200 G18 Q4 201 G19 Q4 202 G20 Q4 203 G21 Q4 204 G22 Q4 205 G23 Q4 206 G24 Q4 207 G25 Q4 208 G26 Q4 209 G27 Q4 210 G28 Q4 211 G29 Q4 212 G30 Q4 213 G31 Q4 214 G32 Q4 215 G33 Q4 216 G34 Q4 217 G35 Q4 218 G36 Q4 219 G37 Q4 220 G38 Q4 221 G39 Q4 222 G40 Q4 223 G41 Q4 224 G42 Q4 225 G43 Q4 226 G44 Q4 227 G45 Q4 228 G46 Q4 229 G47 Q4 230 G48 Q4 231 G49 Q4 232 G50 Q4 233 G51 Q4 234 G52 Q4 235 G53 Q4 236 G54 Q4 237 G55 Q4 238 G56 Q4 239 G57 Q4 240 G58 Q4 241 G59 Q4 242 G60 Q4 243 G61 Q4 244 G62 Q4 245 G63 Q4 246 G64 Q4 247 G65 Q4 248 G66 Q4 249 G67 Q4 250 G68 Q4 251 G69 Q4 252 G70 Q4 253 G71 Q4 254 G72 Q4 255 G73 Q4 256 G74 Q4 257 G75 Q4 258 G76 Q4 259 G77 Q4 260 G78 Q4 261 G79 Q4 262 G80 Q4 263 G81 Q4 264 G82 Q4 265 G83 Q4 266 G84 Q4 267 G85 Q4 268 G86 Q4 269 G87 Q4 270 G1 Q5 271 G2 Q5 272 G3 Q5 273 G4 Q5 274 G5 Q5 275 G6 Q5 276 G7 Q5 277 G8 Q5 278 G9 Q5 279 G10 Q5 280 G11 Q5 281 G12 Q5 282 G13 Q5 283 G14 Q5 284 G15 Q5 285 G16 Q5 286 G17 Q5 287 G18 Q5 288 G19 Q5 289 G20 Q5 290 G21 Q5 291 G22 Q5 292 G23 Q5 293 G24 Q5 294 G25 Q5 295 G26 Q5 296 G27 Q5 297 G28 Q5 298 G29 Q5 299 G30 Q5 300 G31 Q5 301 G32 Q5 302 G33 Q5 303 G34 Q5 304 G35 Q5 305 G36 Q5 306 G37 Q5 307 G38 Q5 308 G39 Q5 309 G40 Q5 310 G41 Q5 311 G42 Q5 312 G43 Q5 313 G44 Q5 314 G45 Q5 315 G46 Q5 316 G47 Q5 317 G48 Q5 318 G49 Q5 319 G50 Q5 320 G51 Q5 321 G52 Q5 322 G53 Q5 323 G54 Q5 324 G55 Q5 325 G56 Q5 326 G57 Q5 327 G58 Q5 328 G59 Q5 329 G60 Q5 330 G61 Q5 331 G62 Q5 332 G63 Q5 333 G64 Q5 334 G65 Q5 335 G66 Q5 336 G67 Q5 337 G68 Q5 338 G69 Q5 339 G70 Q5 340 G71 Q5 341 G72 Q5 342 G73 Q5 343 G74 Q5 344 G75 Q5 345 G76 Q5 346 G77 Q5 347 G78 Q5 348 G79 Q5 349 G80 Q5 350 G81 Q5 351 G82 Q5 352 G83 Q5 353 G84 Q5 354 G85 Q5 355 G86 Q5 356 G87 Q5 357 G1 Q6 358 G2 Q6 359 G3 Q6 360 G4 Q6 361 G5 Q6 362 G6 Q6 363 G7 Q6 364 G8 Q6 365 G9 Q6 366 G10 Q6 367 G11 Q6 368 G12 Q6 369 G13 Q6 370 G14 Q6 371 G15 Q6 372 G16 Q6 373 G17 Q6 374 G18 Q6 375 G19 Q6 376 G20 Q6 377 G21 Q6 378 G22 Q6 379 G23 Q6 380 G24 Q6 381 G25 Q6 382 G26 Q6 383 G27 Q6 384 G28 Q6 385 G29 Q6 386 G30 Q6 387 G31 Q6 388 G32 Q6 389 G33 Q6 390 G34 Q6 391 G35 Q6 392 G36 Q6 393 G37 Q6 394 G38 Q6 395 G39 Q6 396 G40 Q6 397 G41 Q6 398 G42 Q6 399 G43 Q6 400 G44 Q6 401 G45 Q6 402 G46 Q6 403 G47 Q6 404 G48 Q6 405 G49 Q6 406 G50 Q6 407 G51 Q6 408 G52 Q6 409 G53 Q6 410 G54 Q6 411 G55 Q6 412 G56 Q6 413 G57 Q6 414 G58 Q6 415 G59 Q6 416 G60 Q6 417 G61 Q6 418 G62 Q6 419 G63 Q6 420 G64 Q6 421 G65 Q6 422 G66 Q6 423 G67 Q6 424 G68 Q6 425 G69 Q6 426 G70 Q6 427 G71 Q6 428 G72 Q6 429 G73 Q6 430 G74 Q6 431 G75 Q6 432 G76 Q6 433 G77 Q6 434 G78 Q6 435 G79 Q6 436 G80 Q6 437 G81 Q6 438 G82 Q6 439 G83 Q6 440 G84 Q6 441 G85 Q6 442 G86 Q6 443 G87 Q6 444 G1 Q7 445 G2 Q7 446 G3 Q7 447 G4 Q7 448 G5 Q7 449 G6 Q7 450 G7 Q7 451 G8 Q7 452 G9 Q7 453 G10 Q7 454 G11 Q7 455 G12 Q7 456 G13 Q7 457 G14 Q7 458 G15 Q7 459 G16 Q7 460 G17 Q7 461 G18 Q7 462 G19 Q7 463 G20 Q7 464 G21 Q7 465 G22 Q7 466 G23 Q7 467 G24 Q7 468 G25 Q7 469 G26 Q7 470 G27 Q7 471 G28 Q7 472 G29 Q7 473 G30 Q7 474 G31 Q7 475 G32 Q7 476 G33 Q7 477 G34 Q7 478 G35 Q7 479 G36 Q7 480 G37 Q7 481 G38 Q7 482 G39 Q7 483 G40 Q7 484 G41 Q7 485 G42 Q7 486 G43 Q7 487 G44 Q7 488 G45 Q7 489 G46 Q7 490 G47 Q7 491 G48 Q7 492 G49 Q7 493 G50 Q7 494 G51 Q7 495 G52 Q7 496 G53 Q7 497 G54 Q7 498 G55 Q7 499 G56 Q7 500 G57 Q7 501 G58 Q7 502 G59 Q7 503 G60 Q7 504 G61 Q7 505 G62 Q7 506 G63 Q7 507 G64 Q7 508 G65 Q7 509 G66 Q7 510 G67 Q7 511 G68 Q7 512 G69 Q7 513 G70 Q7 514 G71 Q7 515 G72 Q7 516 G73 Q7 517 G74 Q7 518 G75 Q7 519 G76 Q7 520 G77 Q7 521 G78 Q7 522 G79 Q7 523 G80 Q7 524 G81 Q7 525 G82 Q7 526 G83 Q7 527 G84 Q7 528 G85 Q7 529 G86 Q7 530 G87 Q7 531 G1 Q8 532 G2 Q8 533 G3 Q8 534 G4 Q8 535 G5 Q8 536 G6 Q8 537 G7 Q8 538 G8 Q8 539 G9 Q8 540 G10 Q8 541 G11 Q8 542 G12 Q8 543 G13 Q8 544 G14 Q8 545 G15 Q8 546 G16 Q8 547 G17 Q8 548 G18 Q8 549 G19 Q8 550 G20 Q8 551 G21 Q8 552 G22 Q8 553 G23 Q8 554 G24 Q8 555 G25 Q8 556 G26 Q8 557 G27 Q8 558 G28 Q8 559 G29 Q8 560 G30 Q8 561 G31 Q8 562 G32 Q8 563 G33 Q8 564 G34 Q8 565 G35 Q8 566 G36 Q8 567 G37 Q8 568 G38 Q8 569 G39 Q8 570 G40 Q8 571 G41 Q8 572 G42 Q8 573 G43 Q8 574 G44 Q8 575 G45 Q8 576 G46 Q8 577 G47 Q8 578 G48 Q8 579 G49 Q8 580 G50 Q8 581 G51 Q8 582 G52 Q8 583 G53 Q8 584 G54 Q8 585 G55 Q8 586 G56 Q8 587 G57 Q8 588 G58 Q8 589 G59 Q8 590 G60 Q8 591 G61 Q8 592 G62 Q8 593 G63 Q8 594 G64 Q8 595 G65 Q8 596 G66 Q8 597 G67 Q8 598 G68 Q8 599 G69 Q8 600 G70 Q8 601 G71 Q8 602 G72 Q8 603 G73 Q8 604 G74 Q8 605 G75 Q8 606 G76 Q8 607 G77 Q8 608 G78 Q8 609 G79 Q8 610 G80 Q8 611 G81 Q8 612 G82 Q8 613 G83 Q8 614 G84 Q8 615 G85 Q8 616 G86 Q8 617 G87 Q8 618 G1 Q9 619 G2 Q9 620 G3 Q9 621 G4 Q9 622 G5 Q9 623 G6 Q9 624 G7 Q9 625 G8 Q9 626 G9 Q9 627 G10 Q9 628 G11 Q9 629 G12 Q9 630 G13 Q9 631 G14 Q9 632 G15 Q9 633 G16 Q9 634 G17 Q9 635 G18 Q9 636 G19 Q9 637 G20 Q9 638 G21 Q9 639 G22 Q9 640 G23 Q9 641 G24 Q9 642 G25 Q9 643 G26 Q9 644 G27 Q9 645 G28 Q9 646 G29 Q9 647 G30 Q9 648 G31 Q9 649 G32 Q9 650 G33 Q9 651 G34 Q9 652 G35 Q9 653 G36 Q9 654 G37 Q9 655 G38 Q9 656 G39 Q9 657 G40 Q9 658 G41 Q9 659 G42 Q9 660 G43 Q9 661 G44 Q9 662 G45 Q9 663 G46 Q9 664 G47 Q9 665 G48 Q9 666 G49 Q9 667 G50 Q9 668 G51 Q9 669 G52 Q9 670 G53 Q9 671 G54 Q9 672 G55 Q9 673 G56 Q9 674 G57 Q9 675 G58 Q9 676 G59 Q9 677 G60 Q9 678 G61 Q9 679 G62 Q9 680 G63 Q9 681 G64 Q9 682 G65 Q9 683 G66 Q9 684 G67 Q9 685 G68 Q9 686 G69 Q9 687 G70 Q9 688 G71 Q9 689 G72 Q9 690 G73 Q9 691 G74 Q9 692 G75 Q9 693 G76 Q9 694 G77 Q9 695 G78 Q9 696 G79 Q9 697 G80 Q9 698 G81 Q9 699 G82 Q9 700 G83 Q9 701 G84 Q9 702 G85 Q9 703 G86 Q9 704 G87 Q9 705 G1 Q10 706 G2 Q10 707 G3 Q10 708 G4 Q10 709 G5 Q10 710 G6 Q10 711 G7 Q10 712 G8 Q10 713 G9 Q10 714 G10 Q10 715 G11 Q10 716 G12 Q10 717 G13 Q10 718 G14 Q10 719 G15 Q10 720 G16 Q10 721 G17 Q10 722 G18 Q10 723 G19 Q10 724 G20 Q10 725 G21 Q10 726 G22 Q10 727 G23 Q10 728 G24 Q10 729 G25 Q10 730 G26 Q10 731 G27 Q10 732 G28 Q10 733 G29 Q10 734 G30 Q10 735 G31 Q10 736 G32 Q10 737 G33 Q10 738 G34 Q10 739 G35 Q10 740 G36 Q10 741 G37 Q10 742 G38 Q10 743 G39 Q10 744 G40 Q10 745 G41 Q10 746 G42 Q10 747 G43 Q10 748 G44 Q10 749 G45 Q10 750 G46 Q10 751 G47 Q10 752 G48 Q10 753 G49 Q10 754 G50 Q10 755 G51 Q10 756 G52 Q10 757 G53 Q10 758 G54 Q10 759 G55 Q10 760 G56 Q10 761 G57 Q10 762 G58 Q10 763 G59 Q10 764 G60 Q10 765 G61 Q10 766 G62 Q10 767 G63 Q10 768 G64 Q10 769 G65 Q10 770 G66 Q10 771 G67 Q10 772 G68 Q10 773 G69 Q10 774 G70 Q10 775 G71 Q10 776 G72 Q10 777 G73 Q10 778 G74 Q10 779 G75 Q10 780 G76 Q10 781 G77 Q10 782 G78 Q10 783 G79 Q10 784 G80 Q10 785 G81 Q10 786 G82 Q10 787 G83 Q10 788 G84 Q10 789 G85 Q10 790 G86 Q10 791 G87 Q10 792 G1 Q11 793 G2 Q11 794 G3 Q11 795 G4 Q11 796 G5 Q11 797 G6 Q11 798 G7 Q11 799 G8 Q11 800 G9 Q11 801 G10 Q11 802 G11 Q11 803 G12 Q11 804 G13 Q11 805 G14 Q11 806 G15 Q11 807 G16 Q11 808 G17 Q11 809 G18 Q11 810 G19 Q11 811 G20 Q11 812 G21 Q11 813 G22 Q11 814 G23 Q11 815 G24 Q11 816 G25 Q11 817 G26 Q11 818 G27 Q11 819 G28 Q11 820 G29 Q11 821 G30 Q11 822 G31 Q11 823 G32 Q11 824 G33 Q11 825 G34 Q11 826 G35 Q11 827 G36 Q11 828 G37 Q11 829 G38 Q11 830 G39 Q11 831 G40 Q11 832 G41 Q11 833 G42 Q11 834 G43 Q11 835 G44 Q11 836 G45 Q11 837 G46 Q11 838 G47 Q11 839 G48 Q11 840 G49 Q11 841 G50 Q11 842 G51 Q11 843 G52 Q11 844 G53 Q11 845 G54 Q11 846 G55 Q11 847 G56 Q11 848 G57 Q11 849 G58 Q11 850 G59 Q11 851 G60 Q11 852 G61 Q11 853 G62 Q11 854 G63 Q11 855 G64 Q11 856 G65 Q11 857 G66 Q11 858 G67 Q11 859 G68 Q11 860 G69 Q11 861 G70 Q11 862 G71 Q11 863 G72 Q11 864 G73 Q11 865 G74 Q11 866 G75 Q11 867 G76 Q11 868 G77 Q11 869 G78 Q11 870 G79 Q11 871 G80 Q11 872 G81 Q11 873 G82 Q11 874 G83 Q11 875 G84 Q11 876 G85 Q11 877 G86 Q11 878 G87 Q11 879 G1 Q12 880 G2 Q12 881 G3 Q12 882 G4 Q12 883 G5 Q12 884 G6 Q12 885 G7 Q12 886 G8 Q12 887 G9 Q12 888 G10 Q12 889 G11 Q12 890 G12 Q12 891 G13 Q12 892 G14 Q12 893 G15 Q12 894 G16 Q12 895 G17 Q12 896 G18 Q12 897 G19 Q12 898 G20 Q12 899 G21 Q12 900 G22 Q12 901 G23 Q12 902 G24 Q12 903 G25 Q12 904 G26 Q12 905 G27 Q12 906 G28 Q12 907 G29 Q12 908 G30 Q12 909 G31 Q12 910 G32 Q12 911 G33 Q12 912 G34 Q12 913 G35 Q12 914 G36 Q12 915 G37 Q12 916 G38 Q12 917 G39 Q12 918 G40 Q12 919 G41 Q12 920 G42 Q12 921 G43 Q12 922 G44 Q12 923 G45 Q12 924 G46 Q12 925 G47 Q12 926 G48 Q12 927 G49 Q12 928 G50 Q12 929 G51 Q12 930 G52 Q12 931 G53 Q12 932 G54 Q12 933 G55 Q12 934 G56 Q12 935 G57 Q12 936 G58 Q12 937 G59 Q12 938 G60 Q12 939 G61 Q12 940 G62 Q12 941 G63 Q12 942 G64 Q12 943 G65 Q12 944 G66 Q12 945 G67 Q12 946 G68 Q12 947 G69 Q12 948 G70 Q12 949 G71 Q12 950 G72 Q12 951 G73 Q12 952 G74 Q12 953 G75 Q12 954 G76 Q12 955 G77 Q12 956 G78 Q12 957 G79 Q12 958 G80 Q12 959 G81 Q12 960 G82 Q12 961 G83 Q12 962 G84 Q12 963 G85 Q12 964 G86 Q12 965 G87 Q12 966 G1 Q13 967 G2 Q13 968 G3 Q13 969 G4 Q13 970 G5 Q13 971 G6 Q13 972 G7 Q13 973 G8 Q13 974 G9 Q13 975 G10 Q13 976 G11 Q13 977 G12 Q13 978 G13 Q13 979 G14 Q13 980 G15 Q13 981 G16 Q13 982 G17 Q13 983 G18 Q13 984 G19 Q13 985 G20 Q13 986 G21 Q13 987 G22 Q13 988 G23 Q13 989 G24 Q13 990 G25 Q13 991 G26 Q13 992 G27 Q13 993 G28 Q13 994 G29 Q13 995 G30 Q13 996 G31 Q13 997 G32 Q13 998 G33 Q13 999 G34 Q13 1000 G35 Q13 1001 G36 Q13 1002 G37 Q13 1003 G38 Q13 1004 G39 Q13 1005 G40 Q13 1006 G41 Q13 1007 G42 Q13 1008 G43 Q13 1009 G44 Q13 1010 G45 Q13 1011 G46 Q13 1012 G47 Q13 1013 G48 Q13 1014 G49 Q13 1015 G50 Q13 1016 G51 Q13 1017 G52 Q13 1018 G53 Q13 1019 G54 Q13 1020 G55 Q13 1021 G56 Q13 1022 G57 Q13 1023 G58 Q13 1024 G59 Q13 1025 G60 Q13 1026 G61 Q13 1027 G62 Q13 1028 G63 Q13 1029 G64 Q13 1030 G65 Q13 1031 G66 Q13 1032 G67 Q13 1033 G68 Q13 1034 G69 Q13 1035 G70 Q13 1036 G71 Q13 1037 G72 Q13 1038 G73 Q13 1039 G74 Q13 1040 G75 Q13 1041 G76 Q13 1042 G77 Q13 1043 G78 Q13 1044 G79 Q13 1045 G80 Q13 1046 G81 Q13 1047 G82 Q13 1048 G83 Q13 1049 G84 Q13 1050 G85 Q13 1051 G86 Q13 1052 G87 Q13 1053 G1 Q14 1054 G2 Q14 1055 G3 Q14 1056 G4 Q14 1057 G5 Q14 1058 G6 Q14 1059 G7 Q14 1060 G8 Q14 1061 G9 Q14 1062 G10 Q14 1063 G11 Q14 1064 G12 Q14 1065 G13 Q14 1066 G14 Q14 1067 G15 Q14 1068 G16 Q14 1069 G17 Q14 1070 G18 Q14 1071 G19 Q14 1072 G20 Q14 1073 G21 Q14 1074 G22 Q14 1075 G23 Q14 1076 G24 Q14 1077 G25 Q14 1078 G26 Q14 1079 G27 Q14 1080 G28 Q14 1081 G29 Q14 1082 G30 Q14 1083 G31 Q14 1084 G32 Q14 1085 G33 Q14 1086 G34 Q14 1087 G35 Q14 1088 G36 Q14 1089 G37 Q14 1090 G38 Q14 1091 G39 Q14 1092 G40 Q14 1093 G41 Q14 1094 G42 Q14 1095 G43 Q14 1096 G44 Q14 1097 G45 Q14 1098 G46 Q14 1099 G47 Q14 1100 G48 Q14 1101 G49 Q14 1102 G50 Q14 1103 G51 Q14 1104 G52 Q14 1105 G53 Q14 1106 G54 Q14 1107 G55 Q14 1108 G56 Q14 1109 G57 Q14 1110 G58 Q14 1111 G59 Q14 1112 G60 Q14 1113 G61 Q14 1114 G62 Q14 1115 G63 Q14 1116 G64 Q14 1117 G65 Q14 1118 G66 Q14 1119 G67 Q14 1120 G68 Q14 1121 G69 Q14 1122 G70 Q14 1123 G71 Q14 1124 G72 Q14 1125 G73 Q14 1126 G74 Q14 1127 G75 Q14 1128 G76 Q14 1129 G77 Q14 1130 G78 Q14 1131 G79 Q14 1132 G80 Q14 1133 G81 Q14 1134 G82 Q14 1135 G83 Q14 1136 G84 Q14 1137 G85 Q14 1138 G86 Q14 1139 G87 Q14 1140 G1 Q15 1141 G2 Q15 1142 G3 Q15 1143 G4 Q15 1144 G5 Q15 1145 G6 Q15 1146 G7 Q15 1147 G8 Q15 1148 G9 Q15 1149 G10 Q15 1150 G11 Q15 1151 G12 Q15 1152 G13 Q15 1153 G14 Q15 1154 G15 Q15 1155 G16 Q15 1156 G17 Q15 1157 G18 Q15 1158 G19 Q15 1159 G20 Q15 1160 G21 Q15 1161 G22 Q15 1162 G23 Q15 1163 G24 Q15 1164 G25 Q15 1165 G26 Q15 1166 G27 Q15 1167 G28 Q15 1168 G29 Q15 1169 G30 Q15 1170 G31 Q15 1171 G32 Q15 1172 G33 Q15 1173 G34 Q15 1174 G35 Q15 1175 G36 Q15 1176 G37 Q15 1177 G38 Q15 1178 G39 Q15 1179 G40 Q15 1180 G41 Q15 1181 G42 Q15 1182 G43 Q15 1183 G44 Q15 1184 G45 Q15 1185 G46 Q15 1186 G47 Q15 1187 G48 Q15 1188 G49 Q15 1189 G50 Q15 1190 G51 Q15 1191 G52 Q15 1192 G53 Q15 1193 G54 Q15 1194 G55 Q15 1195 G56 Q15 1196 G57 Q15 1197 G58 Q15 1198 G59 Q15 1199 G60 Q15 1200 G61 Q15 1201 G62 Q15 1202 G63 Q15 1203 G64 Q15 1204 G65 Q15 1205 G66 Q15 1206 G67 Q15 1207 G68 Q15 1208 G69 Q15 1209 G70 Q15 1210 G71 Q15 1211 G72 Q15 1212 G73 Q15 1213 G74 Q15 1214 G75 Q15 1215 G76 Q15 1216 G77 Q15 1217 G78 Q15 1218 G79 Q15 1219 G80 Q15 1220 G81 Q15 1221 G82 Q15 1222 G83 Q15 1223 G84 Q15 1224 G85 Q15 1225 G86 Q15 1226 G87 Q15 1227 G1 Q16 1228 G2 Q16 1229 G3 Q16 1230 G4 Q16 1231 G5 Q16 1232 G6 Q16 1233 G7 Q16 1234 G8 Q16 1235 G9 Q16 1236 G10 Q16 1237 G11 Q16 1238 G12 Q16 1239 G13 Q16 1240 G14 Q16 1241 G15 Q16 1242 G16 Q16 1243 G17 Q16 1244 G18 Q16 1245 G19 Q16 1246 G20 Q16 1247 G21 Q16 1248 G22 Q16 1249 G23 Q16 1250 G24 Q16 1251 G25 Q16 1252 G26 Q16 1253 G27 Q16 1254 G28 Q16 1255 G29 Q16 1256 G30 Q16 1257 G31 Q16 1258 G32 Q16 1259 G33 Q16 1260 G34 Q16 1261 G35 Q16 1262 G36 Q16 1263 G37 Q16 1264 G38 Q16 1265 G39 Q16 1266 G40 Q16 1267 G41 Q16 1268 G42 Q16 1269 G43 Q16 1270 G44 Q16 1271 G45 Q16 1272 G46 Q16 1273 G47 Q16 1274 G48 Q16 1275 G49 Q16 1276 G50 Q16 1277 G51 Q16 1278 G52 Q16 1279 G53 Q16 1280 G54 Q16 1281 G55 Q16 1282 G56 Q16 1283 G57 Q16 1284 G58 Q16 1285 G59 Q16 1286 G60 Q16 1287 G61 Q16 1288 G62 Q16 1289 G63 Q16 1290 G64 Q16 1291 G65 Q16 1292 G66 Q16 1293 G67 Q16 1294 G68 Q16 1295 G69 Q16 1296 G70 Q16 1297 G71 Q16 1298 G72 Q16 1299 G73 Q16 1300 G74 Q16 1301 G75 Q16 1302 G76 Q16 1303 G77 Q16 1304 G78 Q16 1305 G79 Q16 1306 G80 Q16 1307 G81 Q16 1308 G82 Q16 1309 G83 Q16 1310 G84 Q16 1311 G85 Q16 1312 G86 Q16 1313 G87 Q16 1314 G1 Q17 1315 G2 Q17 1316 G3 Q17 1317 G4 Q17 1318 G5 Q17 1319 G6 Q17 1320 G7 Q17 1321 G8 Q17 1322 G9 Q17 1323 G10 Q17 1324 G11 Q17 1325 G12 Q17 1326 G13 Q17 1327 G14 Q17 1328 G15 Q17 1329 G16 Q17 1330 G17 Q17 1331 G18 Q17 1332 G19 Q17 1333 G20 Q17 1334 G21 Q17 1335 G22 Q17 1336 G23 Q17 1337 G24 Q17 1338 G25 Q17 1339 G26 Q17 1340 G27 Q17 1341 G28 Q17 1342 G29 Q17 1343 G30 Q17 1344 G31 Q17 1345 G32 Q17 1346 G33 Q17 1347 G34 Q17 1348 G35 Q17 1349 G36 Q17 1350 G37 Q17 1351 G38 Q17 1352 G39 Q17 1353 G40 Q17 1354 G41 Q17 1355 G42 Q17 1356 G43 Q17 1357 G44 Q17 1358 G45 Q17 1359 G46 Q17 1360 G47 Q17 1361 G48 Q17 1362 G49 Q17 1363 G50 Q17 1364 G51 Q17 1365 G52 Q17 1366 G53 Q17 1367 G54 Q17 1368 G55 Q17 1369 G56 Q17 1370 G57 Q17 1371 G58 Q17 1372 G59 Q17 1373 G60 Q17 1374 G61 Q17 1375 G62 Q17 1376 G63 Q17 1377 G64 Q17 1378 G65 Q17 1379 G66 Q17 1380 G67 Q17 1381 G68 Q17 1382 G69 Q17 1383 G70 Q17 1384 G71 Q17 1385 G72 Q17 1386 G73 Q17 1387 G74 Q17 1388 G75 Q17 1389 G76 Q17 1390 G77 Q17 1391 G78 Q17 1392 G79 Q17 1393 G80 Q17 1394 G81 Q17 1395 G82 Q17 1396 G83 Q17 1397 G84 Q17 1398 G85 Q17 1399 G86 Q17 1400 G87 Q17 1401 G1 Q18 1402 G2 Q18 1403 G3 Q18 1404 G4 Q18 1405 G5 Q18 1406 G6 Q18 1407 G7 Q18 1408 G8 Q18 1409 G9 Q18 1410 G10 Q18 1411 G11 Q18 1412 G12 Q18 1413 G13 Q18 1414 G14 Q18 1415 G15 Q18 1416 G16 Q18 1417 G17 Q18 1418 G18 Q18 1419 G19 Q18 1420 G20 Q18 1421 G21 Q18 1422 G22 Q18 1423 G23 Q18 1424 G24 Q18 1425 G25 Q18 1426 G26 Q18 1427 G27 Q18 1428 G28 Q18 1429 G29 Q18 1430 G30 Q18 1431 G31 Q18 1432 G32 Q18 1433 G33 Q18 1434 G34 Q18 1435 G35 Q18 1436 G36 Q18 1437 G37 Q18 1438 G38 Q18 1439 G39 Q18 1440 G40 Q18 1441 G41 Q18 1442 G42 Q18 1443 G43 Q18 1444 G44 Q18 1445 G45 Q18 1446 G46 Q18 1447 G47 Q18 1448 G48 Q18 1449 G49 Q18 1450 G50 Q18 1451 G51 Q18 1452 G52 Q18 1453 G53 Q18 1454 G54 Q18 1455 G55 Q18 1456 G56 Q18 1457 G57 Q18 1458 G58 Q18 1459 G59 Q18 1460 G60 Q18 1461 G61 Q18 1462 G62 Q18 1463 G63 Q18 1464 G64 Q18 1465 G65 Q18 1466 G66 Q18 1467 G67 Q18 1468 G68 Q18 1469 G69 Q18 1470 G70 Q18 1471 G71 Q18 1472 G72 Q18 1473 G73 Q18 1474 G74 Q18 1475 G75 Q18 1476 G76 Q18 1477 G77 Q18 1478 G78 Q18 1479 G79 Q18 1480 G80 Q18 1481 G81 Q18 1482 G82 Q18 1483 G83 Q18 1484 G84 Q18 1485 G85 Q18 1486 G86 Q18 1487 G87 Q18 1488 G1 Q19 1489 G2 Q19 1490 G3 Q19 1491 G4 Q19 1492 G5 Q19 1493 G6 Q19 1494 G7 Q19 1495 G8 Q19 1496 G9 Q19 1497 G10 Q19 1498 G11 Q19 1499 G12 Q19 1500 G13 Q19 1501 G14 Q19 1502 G15 Q19 1503 G16 Q19 1504 G17 Q19 1505 G18 Q19 1506 G19 Q19 1507 G20 Q19 1508 G21 Q19 1509 G22 Q19 1510 G23 Q19 1511 G24 Q19 1512 G25 Q19 1513 G26 Q19 1514 G27 Q19 1515 G28 Q19 1516 G29 Q19 1517 G30 Q19 1518 G31 Q19 1519 G32 Q19 1520 G33 Q19 1521 G34 Q19 1522 G35 Q19 1523 G36 Q19 1524 G37 Q19 1525 G38 Q19 1526 G39 Q19 1527 G40 Q19 1528 G41 Q19 1529 G42 Q19 1530 G43 Q19 1531 G44 Q19 1532 G45 Q19 1533 G46 Q19 1534 G47 Q19 1535 G48 Q19 1536 G49 Q19 1537 G50 Q19 1538 G51 Q19 1539 G52 Q19 1540 G53 Q19 1541 G54 Q19 1542 G55 Q19 1543 G56 Q19 1544 G57 Q19 1545 G58 Q19 1546 G59 Q19 1547 G60 Q19 1548 G61 Q19 1549 G62 Q19 1550 G63 Q19 1551 G64 Q19 1552 G65 Q19 1553 G66 Q19 1554 G67 Q19 1555 G68 Q19 1556 G69 Q19 1557 G70 Q19 1558 G71 Q19 1559 G72 Q19 1560 G73 Q19 1561 G74 Q19 1562 G75 Q19 1563 G76 Q19 1564 G77 Q19 1565 G78 Q19 1566 G79 Q19 1567 G80 Q19 1568 G81 Q19 1569 G82 Q19 1570 G83 Q19 1571 G84 Q19 1572 G85 Q19 1573 G86 Q19 1574 G87 Q19 1575 G2 Q20 1576 G3 Q20 1577 G4 Q20 1578 G5 Q20 1579 G6 Q20 1580 G7 Q20 1581 G8 Q20 1582 G9 Q20 1583 G10 Q20 1584 G12 Q20 1585 G13 Q20 1586 G14 Q20 1587 G15 Q20 1588 G16 Q20 1589 G17 Q20 1590 G18 Q20 1591 G19 Q20 1592 G20 Q20 1593 G21 Q20 1594 G22 Q20 1595 G23 Q20 1596 G24 Q20 1597 G25 Q20 1598 G26 Q20 1599 G27 Q20 1600 G28 Q20 1601 G29 Q20 1602 G30 Q20 1603 G31 Q20 1604 G32 Q20 1605 G33 Q20 1606 G34 Q20 1607 G35 Q20 1608 G36 Q20 1609 G37 Q20 1610 G38 Q20 1611 G39 Q20 1612 G40 Q20 1613 G41 Q20 1614 G42 Q20 1615 G43 Q20 1616 G44 Q20 1617 G45 Q20 1618 G46 Q20 1619 G47 Q20 1620 G48 Q20 1621 G49 Q20 1622 G50 Q20 1623 G51 Q20 1624 G52 Q20 1625 G53 Q20 1626 G54 Q20 1627 G55 Q20 1628 G56 Q20 1629 G57 Q20 1630 G58 Q20 1631 G59 Q20 1632 G60 Q20 1633 G61 Q20 1634 G62 Q20 1635 G63 Q20 1636 G64 Q20 1637 G65 Q20 1638 G66 Q20 1639 G67 Q20 1640 G68 Q20 1641 G69 Q20 1642 G70 Q20 1643 G71 Q20 1644 G72 Q20 1645 G73 Q20 1646 G74 Q20 1647 G75 Q20 1648 G76 Q20 1649 G77 Q20 1650 G78 Q20 1651 G79 Q20 1652 G80 Q20 1653 G81 Q20 1654 G82 Q20 1655 G83 Q20 1656 G84 Q20 1657 G85 Q20 1658 G86 Q20 1659 G87 Q20 1660 G1 Q21 1661 G2 Q21 1662 G3 Q21 1663 G4 Q21 1664 G5 Q21 1665 G6 Q21 1666 G7 Q21 1667 G8 Q21 1668 G9 Q21 1669 G10 Q21 1670 G11 Q21 1671 G12 Q21 1672 G13 Q21 1673 G14 Q21 1674 G15 Q21 1675 G16 Q21 1676 G17 Q21 1677 G18 Q21 1678 G19 Q21 1679 G20 Q21 1680 G21 Q21 1681 G22 Q21 1682 G23 Q21 1683 G24 Q21 1684 G25 Q21 1685 G26 Q21 1686 G27 Q21 1687 G28 Q21 1688 G29 Q21 1689 G30 Q21 1690 G31 Q21 1691 G32 Q21 1692 G33 Q21 1693 G34 Q21 1694 G35 Q21 1695 G36 Q21 1696 G37 Q21 1697 G38 Q21 1698 G39 Q21 1699 G40 Q21 1700 G41 Q21 1701 G42 Q21 1702 G43 Q21 1703 G44 Q21 1704 G45 Q21 1705 G46 Q21 1706 G47 Q21 1707 G48 Q21 1708 G49 Q21 1709 G50 Q21 1710 G51 Q21 1711 G52 Q21 1712 G53 Q21 1713 G54 Q21 1714 G55 Q21 1715 G56 Q21 1716 G57 Q21 1717 G58 Q21 1718 G59 Q21 1719 G60 Q21 1720 G61 Q21 1721 G62 Q21 1722 G63 Q21 1723 G64 Q21 1724 G65 Q21 1725 G66 Q21 1726 G67 Q21 1727 G68 Q21 1728 G69 Q21 1729 G70 Q21 1730 G71 Q21 1731 G72 Q21 1732 G73 Q21 1733 G74 Q21 1734 G75 Q21 1735 G76 Q21 1736 G77 Q21 1737 G78 Q21 1738 G79 Q21 1739 G80 Q21 1740 G81 Q21 1741 G82 Q21 1742 G83 Q21 1743 G84 Q21 1744 G85 Q21 1745 G86 Q21 1746 G87 Q21 1747 G1 Q22 1748 G2 Q22 1749 G3 Q22 1750 G4 Q22 1751 G5 Q22 1752 G6 Q22 1753 G7 Q22 1754 G8 Q22 1755 G9 Q22 1756 G10 Q22 1757 G11 Q22 1758 G12 Q22 1759 G13 Q22 1760 G14 Q22 1761 G15 Q22 1762 G16 Q22 1763 G17 Q22 1764 G18 Q22 1765 G19 Q22 1766 G20 Q22 1767 G21 Q22 1768 G22 Q22 1769 G23 Q22 1770 G24 Q22 1771 G25 Q22 1772 G26 Q22 1773 G27 Q22 1774 G28 Q22 1775 G29 Q22 1776 G30 Q22 1777 G31 Q22 1778 G32 Q22 1779 G33 Q22 1780 G34 Q22 1781 G35 Q22 1782 G36 Q22 1783 G37 Q22 1784 G38 Q22 1785 G39 Q22 1786 G40 Q22 1787 G41 Q22 1788 G42 Q22 1789 G43 Q22 1790 G44 Q22 1791 G45 Q22 1792 G46 Q22 1793 G47 Q22 1794 G48 Q22 1795 G49 Q22 1796 G50 Q22 1797 G51 Q22 1798 G52 Q22 1799 G53 Q22 1800 G54 Q22 1801 G55 Q22 1802 G56 Q22 1803 G57 Q22 1804 G58 Q22 1805 G59 Q22 1806 G60 Q22 1807 G61 Q22 1808 G62 Q22 1809 G63 Q22 1810 G64 Q22 1811 G65 Q22 1812 G66 Q22 1813 G67 Q22 1814 G68 Q22 1815 G69 Q22 1816 G70 Q22 1817 G71 Q22 1818 G72 Q22 1819 G73 Q22 1820 G74 Q22 1821 G75 Q22 1822 G76 Q22 1823 G77 Q22 1824 G78 Q22 1825 G79 Q22 1826 G80 Q22 1827 G81 Q22 1828 G82 Q22 1829 G83 Q22 1830 G84 Q22 1831 G85 Q22 1832 G86 Q22 1833 G87 Q22 1834 G1 Q23 1835 G2 Q23 1836 G3 Q23 1837 G4 Q23 1838 G5 Q23 1839 G6 Q23 1840 G7 Q23 1841 G8 Q23 1842 G9 Q23 1843 G10 Q23 1844 G11 Q23 1845 G12 Q23 1846 G13 Q23 1847 G14 Q23 1848 G15 Q23 1849 G16 Q23 1850 G17 Q23 1851 G18 Q23 1852 G19 Q23 1853 G20 Q23 1854 G21 Q23 1855 G22 Q23 1856 G23 Q23 1857 G24 Q23 1858 G25 Q23 1859 G26 Q23 1860 G27 Q23 1861 G28 Q23 1862 G29 Q23 1863 G30 Q23 1864 G31 Q23 1865 G32 Q23 1866 G33 Q23 1867 G34 Q23 1868 G35 Q23 1869 G36 Q23 1870 G37 Q23 1871 G38 Q23 1872 G39 Q23 1873 G40 Q23 1874 G41 Q23 1875 G42 Q23 1876 G43 Q23 1877 G44 Q23 1878 G45 Q23 1879 G46 Q23 1880 G47 Q23 1881 G48 Q23 1882 G49 Q23 1883 G50 Q23 1884 G51 Q23 1885 G52 Q23 1886 G53 Q23 1887 G54 Q23 1888 G55 Q23 1889 G56 Q23 1890 G57 Q23 1891 G58 Q23 1892 G59 Q23 1893 G60 Q23 1894 G61 Q23 1895 G62 Q23 1896 G63 Q23 1897 G64 Q23 1898 G65 Q23 1899 G66 Q23 1900 G67 Q23 1901 G68 Q23 1902 G69 Q23 1903 G70 Q23 1904 G71 Q23 1905 G72 Q23 1906 G73 Q23 1907 G74 Q23 1908 G75 Q23 1909 G76 Q23 1910 G77 Q23 1911 G78 Q23 1912 G79 Q23 1913 G80 Q23 1914 G81 Q23 1915 G82 Q23 1916 G83 Q23 1917 G84 Q23 1918 G85 Q23 1919 G86 Q23 1920 G87 Q23 1921 G1 Q24 1922 G2 Q24 1923 G3 Q24 1924 G4 Q24 1925 G5 Q24 1926 G6 Q24 1927 G7 Q24 1928 G8 Q24 1929 G9 Q24 1930 G10 Q24 1931 G11 Q24 1932 G12 Q24 1933 G13 Q24 1934 G14 Q24 1935 G15 Q24 1936 G16 Q24 1937 G17 Q24 1938 G18 Q24 1939 G19 Q24 1940 G20 Q24 1941 G21 Q24 1942 G22 Q24 1943 G23 Q24 1944 G24 Q24 1945 G25 Q24 1946 G26 Q24 1947 G27 Q24 1948 G28 Q24 1949 G29 Q24 1950 G30 Q24 1951 G31 Q24 1952 G32 Q24 1953 G33 Q24 1954 G34 Q24 1955 G35 Q24 1956 G36 Q24 1957 G37 Q24 1958 G38 Q24 1959 G39 Q24 1960 G40 Q24 1961 G41 Q24 1962 G42 Q24 1963 G43 Q24 1964 G44 Q24 1965 G45 Q24 1966 G46 Q24 1967 G47 Q24 1968 G48 Q24 1969 G49 Q24 1970 G50 Q24 1971 G51 Q24 1972 G52 Q24 1973 G53 Q24 1974 G54 Q24 1975 G55 Q24 1976 G56 Q24 1977 G57 Q24 1978 G58 Q24 1979 G59 Q24 1980 G60 Q24 1981 G61 Q24 1982 G62 Q24 1983 G63 Q24 1984 G64 Q24 1985 G65 Q24 1986 G66 Q24 1987 G67 Q24 1988 G68 Q24 1989 G69 Q24 1990 G70 Q24 1991 G71 Q24 1992 G72 Q24 1993 G73 Q24 1994 G74 Q24 1995 G75 Q24 1996 G76 Q24 1997 G77 Q24 1998 G78 Q24 1999 G79 Q24 2000 G80 Q24 2001 G81 Q24 2002 G82 Q24 2003 G83 Q24 2004 G84 Q24 2005 G85 Q24 2006 G86 Q24 2007 G87 Q24 2008 G1 Q25 2009 G2 Q25 2010 G3 Q25 2011 G4 Q25 2012 G5 Q25 2013 G6 Q25 2014 G7 Q25 2015 G8 Q25 2016 G9 Q25 2017 G10 Q25 2018 G11 Q25 2019 G12 Q25 2020 G13 Q25 2021 G14 Q25 2022 G15 Q25 2023 G16 Q25 2024 G17 Q25 2025 G18 Q25 2026 G19 Q25 2027 G20 Q25 2028 G21 Q25 2029 G22 Q25 2030 G23 Q25 2031 G24 Q25 2032 G25 Q25 2033 G26 Q25 2034 G27 Q25 2035 G28 Q25 2036 G29 Q25 2037 G30 Q25 2038 G31 Q25 2039 G32 Q25 2040 G33 Q25 2041 G34 Q25 2042 G35 Q25 2043 G36 Q25 2044 G37 Q25 2045 G38 Q25 2046 G39 Q25 2047 G40 Q25 2048 G41 Q25 2049 G42 Q25 2050 G43 Q25 2051 G44 Q25 2052 G45 Q25 2053 G46 Q25 2054 G47 Q25 2055 G48 Q25 2056 G49 Q25 2057 G50 Q25 2058 G51 Q25 2059 G52 Q25 2060 G53 Q25 2061 G54 Q25 2062 G55 Q25 2063 G56 Q25 2064 G57 Q25 2065 G58 Q25 2066 G59 Q25 2067 G60 Q25 2068 G61 Q25 2069 G62 Q25 2070 G63 Q25 2071 G64 Q25 2072 G65 Q25 2073 G66 Q25 2074 G67 Q25 2075 G68 Q25 2076 G69 Q25 2077 G70 Q25 2078 G71 Q25 2079 G72 Q25 2080 G73 Q25 2081 G74 Q25 2082 G75 Q25 2083 G76 Q25 2084 G77 Q25 2085 G78 Q25 2086 G79 Q25 2087 G80 Q25 2088 G81 Q25 2089 G82 Q25 2090 G83 Q25 2091 G84 Q25 2092 G85 Q25 2093 G86 Q25 2094 G87 Q25

EXAMPLES 2095-2442

The procedure is as in Examples 7-9, but the following compounds of formula [G⁺].[X^(m−)]_(p).[Y^(n+)]_(q) (XI), which can be prepared analogously to Examples 1-6, are used:

Ex. G⁺ X^(m−) p Y^(n+) q 2095 G1 Q1 ½ 0 2096 G2 Q1 ½ 0 2097 G3 Q1 ½ 0 2098 G4 Q1 ½ 0 2099 G5 Q1 ½ 0 2100 G6 Q1 ½ 0 2101 G7 Q1 ½ 0 2102 G8 Q1 ½ 0 2103 G9 Q1 ½ 0 2104 G10 Q1 ½ 0 2105 G11 Q1 ½ 0 2106 G12 Q1 ½ 0 2107 G13 Q1 ½ 0 2108 G14 Q1 ½ 0 2109 G15 Q1 ½ 0 2110 G16 Q1 ½ 0 2111 G17 Q1 ½ 0 2112 G18 Q1 ½ 0 2113 G19 Q1 ½ 0 2114 G20 Q1 ½ 0 2115 G21 Q1 ½ 0 2116 G22 Q1 ½ 0 2117 G23 Q1 ½ 0 2118 G24 Q1 ½ 0 2119 G25 Q1 ½ 0 2120 G26 Q1 ½ 0 2121 G27 Q1 ½ 0 2122 G28 Q1 ½ 0 2123 G29 Q1 ½ 0 2124 G30 Q1 ½ 0 2125 G31 Q1 ½ 0 2126 G32 Q1 ½ 0 2127 G33 Q1 ½ 0 2128 G34 Q1 ½ 0 2129 G35 Q1 ½ 0 2130 G36 Q1 ½ 0 2131 G37 Q1 ½ 0 2132 G38 Q1 ½ 0 2133 G39 Q1 ½ 0 2134 G40 Q1 ½ 0 2135 G41 Q1 ½ 0 2136 G42 Q1 ½ 0 2137 G43 Q1 ½ 0 2138 G44 Q1 ½ 0 2139 G45 Q1 ½ 0 2140 G46 Q1 ½ 0 2141 G47 Q1 ½ 0 2142 G48 Q1 ½ 0 2143 G49 Q1 ½ 0 2144 G50 Q1 ½ 0 2145 G51 Q1 ½ 0 2146 G52 Q1 ½ 0 2147 G53 Q1 ½ 0 2148 G54 Q1 ½ 0 2149 G55 Q1 ½ 0 2150 G56 Q1 ½ 0 2151 G57 Q1 ½ 0 2152 G58 Q1 ½ 0 2153 G59 Q1 ½ 0 2154 G60 Q1 ½ 0 2155 G61 Q1 ½ 0 2156 G62 Q1 ½ 0 2157 G63 Q1 ½ 0 2158 G64 Q1 ½ 0 2159 G65 Q1 ½ 0 2160 G66 Q1 ½ 0 2161 G67 Q1 ½ 0 2162 G68 Q1 ½ 0 2163 G69 Q1 ½ 0 2164 G70 Q1 ½ 0 2165 G71 Q1 ½ 0 2166 G72 Q1 ½ 0 2167 G73 Q1 ½ 0 2168 G74 Q1 ½ 0 2169 G75 Q1 ½ 0 2170 G76 Q1 ½ 0 2171 G77 Q1 ½ 0 2172 G78 Q1 ½ 0 2173 G79 Q1 ½ 0 2174 G80 Q1 ½ 0 2175 G81 Q1 ½ 0 2176 G82 Q1 ½ 0 2177 G83 Q1 ½ 0 2178 G84 Q1 ½ 0 2179 G85 Q1 ½ 0 2180 G86 Q1 ½ 0 2181 G87 Q1 ½ 0 2182 G1 Q26 ½ 0 2183 G2 Q26 ½ 0 2184 G3 Q26 ½ 0 2185 G4 Q26 ½ 0 2186 G5 Q26 ½ 0 2187 G6 Q26 ½ 0 2188 G7 Q26 ½ 0 2189 G8 Q26 ½ 0 2190 G9 Q26 ½ 0 2191 G10 Q26 ½ 0 2192 G11 Q26 ½ 0 2193 G12 Q26 ½ 0 2194 G13 Q26 ½ 0 2195 G14 Q26 ½ 0 2196 G15 Q26 ½ 0 2197 G16 Q26 ½ 0 2198 G17 Q26 ½ 0 2199 G18 Q26 ½ 0 2200 G19 Q26 ½ 0 2201 G20 Q26 ½ 0 2202 G21 Q26 ½ 0 2203 G22 Q26 ½ 0 2204 G23 Q26 ½ 0 2205 G24 Q26 ½ 0 2206 G25 Q26 ½ 0 2207 G26 Q26 ½ 0 2208 G27 Q26 ½ 0 2209 G28 Q26 ½ 0 2210 G29 Q26 ½ 0 2211 G30 Q26 ½ 0 2212 G31 Q26 ½ 0 2213 G32 Q26 ½ 0 2214 G33 Q26 ½ 0 2215 G34 Q26 ½ 0 2216 G35 Q26 ½ 0 2217 G36 Q26 ½ 0 2218 G37 Q26 ½ 0 2219 G38 Q26 ½ 0 2220 G39 Q26 ½ 0 2221 G40 Q26 ½ 0 2222 G41 Q26 ½ 0 2223 G42 Q26 ½ 0 2224 G43 Q26 ½ 0 2225 G44 Q26 ½ 0 2226 G45 Q26 ½ 0 2227 G46 Q26 ½ 0 2228 G47 Q26 ½ 0 2229 G48 Q26 ½ 0 2230 G49 Q26 ½ 0 2231 G50 Q26 ½ 0 2232 G51 Q26 ½ 0 2233 G52 Q26 ½ 0 2234 G53 Q26 ½ 0 2235 G54 Q26 ½ 0 2236 G55 Q26 ½ 0 2237 G56 Q26 ½ 0 2238 G57 Q26 ½ 0 2239 G58 Q26 ½ 0 2240 G59 Q26 ½ 0 2241 G60 Q26 ½ 0 2242 G61 Q26 ½ 0 2243 G62 Q26 ½ 0 2244 G63 Q26 ½ 0 2245 G64 Q26 ½ 0 2246 G65 Q26 ½ 0 2247 G66 Q26 ½ 0 2248 G67 Q26 ½ 0 2249 G68 Q26 ½ 0 2250 G69 Q26 ½ 0 2251 G70 Q26 ½ 0 2252 G71 Q26 ½ 0 2253 G72 Q26 ½ 0 2254 G73 Q26 ½ 0 2255 G74 Q26 ½ 0 2256 G75 Q26 ½ 0 2257 G76 Q26 ½ 0 2258 G77 Q26 ½ 0 2259 G78 Q26 ½ 0 2260 G79 Q26 ½ 0 2261 G80 Q26 ½ 0 2262 G81 Q26 ½ 0 2263 G82 Q26 ½ 0 2264 G83 Q26 ½ 0 2265 G84 Q26 ½ 0 2266 G85 Q26 ½ 0 2267 G86 Q26 ½ 0 2268 G87 Q26 ½ 0 2269 G1 Q1 1 NH₄ ⁺ 1 2270 G2 Q1 1 NH₄ ⁺ 1 2271 G3 Q1 1 NH₄ ⁺ 1 2272 G4 Q1 1 NH₄ ⁺ 1 2273 G5 Q1 1 NH₄ ⁺ 1 2274 G6 Q1 1 NH₄ ⁺ 1 2275 G7 Q1 1 NH₄ ⁺ 1 2276 G8 Q1 1 NH₄ ⁺ 1 2277 G9 Q1 1 NH₄ ⁺ 1 2278 G10 Q1 1 NH₄ ⁺ 1 2279 G11 Q1 1 NH₄ ⁺ 1 2280 G12 Q1 1 NH₄ ⁺ 1 2281 G13 Q1 1 NH₄ ⁺ 1 2282 G14 Q1 1 NH₄ ⁺ 1 2283 G15 Q1 1 NH₄ ⁺ 1 2284 G16 Q1 1 NH₄ ⁺ 1 2285 G17 Q1 1 NH₄ ⁺ 1 2286 G18 Q1 1 NH₄ ⁺ 1 2287 G19 Q1 1 NH₄ ⁺ 1 2288 G20 Q1 1 NH₄ ⁺ 1 2289 G21 Q1 1 NH₄ ⁺ 1 2290 G22 Q1 1 NH₄ ⁺ 1 2291 G23 Q1 1 NH₄ ⁺ 1 2292 G24 Q1 1 NH₄ ⁺ 1 2293 G25 Q1 1 NH₄ ⁺ 1 2294 G26 Q1 1 NH₄ ⁺ 1 2295 G27 Q1 1 NH₄ ⁺ 1 2296 G28 Q1 1 NH₄ ⁺ 1 2297 G29 Q1 1 NH₄ ⁺ 1 2298 G30 Q1 1 NH₄ ⁺ 1 2299 G31 Q1 1 NH₄ ⁺ 1 2300 G32 Q1 1 NH₄ ⁺ 1 2301 G33 Q1 1 NH₄ ⁺ 1 2302 G34 Q1 1 NH₄ ⁺ 1 2303 G35 Q1 1 NH₄ ⁺ 1 2304 G36 Q1 1 NH₄ ⁺ 1 2305 G37 Q1 1 NH₄ ⁺ 1 2306 G38 Q1 1 NH₄ ⁺ 1 2307 G39 Q1 1 NH₄ ⁺ 1 2308 G40 Q1 1 NH₄ ⁺ 1 2309 G41 Q1 1 NH₄ ⁺ 1 2310 G42 Q1 1 NH₄ ⁺ 1 2311 G43 Q1 1 NH₄ ⁺ 1 2312 G44 Q1 1 NH₄ ⁺ 1 2313 G45 Q1 1 NH₄ ⁺ 1 2314 G46 Q1 1 NH₄ ⁺ 1 2315 G47 Q1 1 NH₄ ⁺ 1 2316 G48 Q1 1 NH₄ ⁺ 1 2317 G49 Q1 1 NH₄ ⁺ 1 2318 G50 Q1 1 NH₄ ⁺ 1 2319 G51 Q1 1 NH₄ ⁺ 1 2320 G52 Q1 1 NH₄ ⁺ 1 2321 G53 Q1 1 NH₄ ⁺ 1 2322 G54 Q1 1 NH₄ ⁺ 1 2323 G55 Q1 1 NH₄ ⁺ 1 2324 G56 Q1 1 NH₄ ⁺ 1 2325 G57 Q1 1 NH₄ ⁺ 1 2326 G58 Q1 1 NH₄ ⁺ 1 2327 G59 Q1 1 NH₄ ⁺ 1 2328 G60 Q1 1 NH₄ ⁺ 1 2329 G61 Q1 1 NH₄ ⁺ 1 2330 G62 Q1 1 NH₄ ⁺ 1 2331 G63 Q1 1 NH₄ ⁺ 1 2332 G64 Q1 1 NH₄ ⁺ 1 2333 G65 Q1 1 NH₄ ⁺ 1 2334 G66 Q1 1 NH₄ ⁺ 1 2335 G67 Q1 1 NH₄ ⁺ 1 2336 G68 Q1 1 NH₄ ⁺ 1 2337 G69 Q1 1 NH₄ ⁺ 1 2338 G70 Q1 1 NH₄ ⁺ 1 2339 G71 Q1 1 NH₄ ⁺ 1 2340 G72 Q1 1 NH₄ ⁺ 1 2341 G73 Q1 1 NH₄ ⁺ 1 2342 G74 Q1 1 NH₄ ⁺ 1 2343 G75 Q1 1 NH₄ ⁺ 1 2344 G76 Q1 1 NH₄ ⁺ 1 2345 G77 Q1 1 NH₄ ⁺ 1 2346 G78 Q1 1 NH₄ ⁺ 1 2347 G79 Q1 1 NH₄ ⁺ 1 2348 G80 Q1 1 NH₄ ⁺ 1 2349 G81 Q1 1 NH₄ ⁺ 1 2350 G82 Q1 1 NH₄ ⁺ 1 2351 G83 Q1 1 NH₄ ⁺ 1 2352 G84 Q1 1 NH₄ ⁺ 1 2353 G85 Q1 1 NH₄ ⁺ 1 2354 G86 Q1 1 NH₄ ⁺ 1 2355 G87 Q1 1 NH₄ ⁺ 1 2356 G1 Q26 1 NH₄ ⁺ 1 2357 G2 Q26 1 NH₄ ⁺ 1 2358 G3 Q26 1 NH₄ ⁺ 1 2359 G4 Q26 1 NH₄ ⁺ 1 2360 G5 Q26 1 NH₄ ⁺ 1 2361 G6 Q26 1 NH₄ ⁺ 1 2362 G7 Q26 1 NH₄ ⁺ 1 2363 G8 Q26 1 NH₄ ⁺ 1 2364 G9 Q26 1 NH₄ ⁺ 1 2365 G10 Q26 1 NH₄ ⁺ 1 2366 G11 Q26 1 NH₄ ⁺ 1 2367 G12 Q26 1 NH₄ ⁺ 1 2368 G13 Q26 1 NH₄ ⁺ 1 2369 G14 Q26 1 NH₄ ⁺ 1 2370 G15 Q26 1 NH₄ ⁺ 1 2371 G16 Q26 1 NH₄ ⁺ 1 2372 G17 Q26 1 NH₄ ⁺ 1 2373 G18 Q26 1 NH₄ ⁺ 1 2374 G19 Q26 1 NH₄ ⁺ 1 2375 G20 Q26 1 NH₄ ⁺ 1 2376 G21 Q26 1 NH₄ ⁺ 1 2377 G22 Q26 1 NH₄ ⁺ 1 2378 G23 Q26 1 NH₄ ⁺ 1 2379 G24 Q26 1 NH₄ ⁺ 1 2380 G25 Q26 1 NH₄ ⁺ 1 2381 G26 Q26 1 NH₄ ⁺ 1 2382 G27 Q26 1 NH₄ ⁺ 1 2383 G28 Q26 1 NH₄ ⁺ 1 2384 G29 Q26 1 NH₄ ⁺ 1 2385 G30 Q26 1 NH₄ ⁺ 1 2386 G31 Q26 1 NH₄ ⁺ 1 2387 G32 Q26 1 NH₄ ⁺ 1 2388 G33 Q26 1 NH₄ ⁺ 1 2389 G34 Q26 1 NH₄ ⁺ 1 2390 G35 Q26 1 NH₄ ⁺ 1 2391 G36 Q26 1 NH₄ ⁺ 1 2392 G37 Q26 1 NH₄ ⁺ 1 2393 G38 Q26 1 NH₄ ⁺ 1 2394 G39 Q26 1 NH₄ ⁺ 1 2395 G40 Q26 1 NH₄ ⁺ 1 2396 G41 Q26 1 NH₄ ⁺ 1 2397 G42 Q26 1 NH₄ ⁺ 1 2398 G43 Q26 1 NH₄ ⁺ 1 2399 G44 Q26 1 NH₄ ⁺ 1 2400 G45 Q26 1 NH₄ ⁺ 1 2401 G46 Q26 1 NH₄ ⁺ 1 2402 G47 Q26 1 NH₄ ⁺ 1 2403 G48 Q26 1 NH₄ ⁺ 1 2404 G49 Q26 1 NH₄ ⁺ 1 2405 G50 Q26 1 NH₄ ⁺ 1 2406 G51 Q26 1 NH₄ ⁺ 1 2407 G52 Q26 1 NH₄ ⁺ 1 2408 G53 Q26 1 NH₄ ⁺ 1 2409 G54 Q26 1 NH₄ ⁺ 1 2410 G55 Q26 1 NH₄ ⁺ 1 2411 G56 Q26 1 NH₄ ⁺ 1 2412 G57 Q26 1 NH₄ ⁺ 1 2413 G58 Q26 1 NH₄ ⁺ 1 2414 G59 Q26 1 NH₄ ⁺ 1 2415 G60 Q26 1 NH₄ ⁺ 1 2416 G61 Q26 1 NH₄ ⁺ 1 2417 G62 Q26 1 NH₄ ⁺ 1 2418 G63 Q26 1 NH₄ ⁺ 1 2419 G64 Q26 1 NH₄ ⁺ 1 2420 G65 Q26 1 NH₄ ⁺ 1 2421 G66 Q26 1 NH₄ ⁺ 1 2422 G67 Q26 1 NH₄ ⁺ 1 2423 G68 Q26 1 NH₄ ⁺ 1 2424 G69 Q26 1 NH₄ ⁺ 1 2425 G70 Q26 1 NH₄ ⁺ 1 2426 G71 Q26 1 NH₄ ⁺ 1 2427 G72 Q26 1 NH₄ ⁺ 1 2428 G73 Q26 1 NH₄ ⁺ 1 2429 G74 Q26 1 NH₄ ⁺ 1 2430 G75 Q26 1 NH₄ ⁺ 1 2431 G76 Q26 1 NH₄ ⁺ 1 2432 G77 Q26 1 NH₄ ⁺ 1 2433 G78 Q26 1 NH₄ ⁺ 1 2434 G79 Q26 1 NH₄ ⁺ 1 2435 G80 Q26 1 NH₄ ⁺ 1 2436 G81 Q26 1 NH₄ ⁺ 1 2437 G82 Q26 1 NH₄ ⁺ 1 2438 G83 Q26 1 NH₄ ⁺ 1 2439 G84 Q26 1 NH₄ ⁺ 1 2440 G85 Q26 1 NH₄ ⁺ 1 2441 G86 Q26 1 NH₄ ⁺ 1 2442 G87 Q26 1 NH₄ ⁺ 1

EXAMPLE 2443

The procedure is as in Examples 7-9, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula

EXAMPLE 2444

The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula

EXAMPLE 2445

The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula

EXAMPLE 2446

The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula

EXAMPLE 2447

The procedure is as in Example 2443, but the product of formula G89 according to Example 4 is used together with 20% by weight (based on the product according to Example G89) of the product of formula

EXAMPLES 2448-2452

The procedure is as in Examples 2443-2447, but the product of formula G90 according to Example 5 is used instead of the product of formula G89 according to Example 4.

EXAMPLE 2453

12.1 g of N-ethylaniline are stirred in 22 ml of 2-chloropropionic acid ethyl ester in the presence of 10.6 ml of sodium carbonate and 0.2 g of potassium iodide until the N-ethylaniline can no longer be detected in thin-layer chromatography. The chloropropionic acid ester is distilled off, and the oil that remains is taken up in ethyl acetate and extracted with water until salt-free. The dried organic phase is concentrated, yielding 20 g of an oily mass of formula:

EXAMPLE 2454

7.1 g of the compound according to Example 2453 are introduced into 20 ml of N,N-dimethylformamide and cooled in an ice bath. 3.2 ml of phosphorus oxytrichloride are then slowly added dropwise and the mixture is stirred first at 20° C., and then for a further 4 hours at 60° C. The cooled reaction mass is discharged into a small amount of ice-water and neutralised with dilute sodium hydroxide solution. The resulting oil is taken up in ethyl acetate and washed with sodium chloride solution. The organic phase is dried and concentrated, yielding 6.7 g of the product of formula:

EXAMPLE 2455

6.7 g of the compound according to Example 2454 are dissolved in 50 ml of methanol, and 0.43 g of sodium borohydride is added. After 30 minutes at 20° C., the starting material can no longer be detected. The reaction solution is freed of methanol by distillation and the residue is taken up in ethyl acetate and washed with concentrated sodium chloride solution. The dried ethyl acetate phase is concentrated by evaporation; yielding 4.6 g of an oil of formula

EXAMPLE 2456

4.25 g of the compound according to Example 2455 are dissolved in 25 ml of dichloromethane, and 2.6 ml of 3-isopropenyl-N,N-dimethylaniline are added. While cooling with an ice bath, 16 ml of a 1M boron trichloride solution in dichloromethane are added and the mixture is left to react overnight in the initial ice-bath to complete the reaction. Then, while cooling in an ice bath, 16 ml of concentrated sulfuric acid are added dropwise. The resulting reaction mixture is discharged onto ice, neutralised with sodium hydroxide solution and taken up in dichloromethane. After being washed, the organic phase is dried and the dichloromethane is distilled off, leaving behind 5.8 g of a blue-green, very oxygen-senstive oil of formula

EXAMPLE 2457

5.8 g of the compound according to Example 2456 are dissolved in 40 ml of 100% acetic acid, and 150 drops of 60% perchloric acid are added. 1.65 g of tetrabutylammonium (meta)periodate are added to the resulting mixture. Stirring is carried out for 3 hours at 40° C., and the reaction mass is discharged into 250 ml of water and 25 g of sodium perchlorate monohydrate and the oily mass obtained is treated with a potassium perchlorate solution. After working up, 3.4 g of crude product are obtained. Repeated chromatographic purification of the crude product yields the analytically pure compound of the following formula:

EXAMPLE 2458

1.33 g of analytically pure product according to Example 2457 are dissolved in acetone with 2.78 g of the cobalt complex of structure Q20 and the solution is concentrated by evaporation. The residue is taken up in methylene chloride, extracted by shaking repeatedly with deionised water and, without drying of the organic phase, concentrated to dryness without residue, yielding 3.13 g of compound of formula:

EXAMPLE 2459

The procedure is as in Example 7, but instead of the product according to Example 1 there is used an equal amount of the product according to Example 2458. The absorption maximum of a recording support produced analogously to Example 7 is at 623 nm.

EXAMPLE 2460

2.7 g of 4-fluorobenzaldehyde are stirred at 110° C. in 20 ml of dimethyl sulfoxide with 3.74 g of morpholine and 3 g of potassium carbonate for 6 hours. Customary working-up yields 0.95 g of crystalline product of formula

That product is processed further analogously to Examples 2455 to 2458; yielding the compound of formula:

EXAMPLE 2461

The procedure is as in Example 7, but instead of the product according to Example 1 there is used an equal amount of the product according to Example 2460. The absorption maximum of a recording support produced analogously to Example 7 is at 626 nm.

EXAMPLE 2462

The procedure is as in Example 7, but instead of the product according to Example 1 there is used an equal amount of the product according to Example 3. The absorption maximum of the recording support is at 625 nm.

EXAMPLE 2463

The procedure is as in Example 3, but instead of the metal complex of formula Q20 there is used an equimolar amount of the metal complex of formula Q16. The absorption maximum of a recording support produced analogously to Example 7 is at 631 nm.

EXAMPLE 2464

The procedure is as in Example 1, but instead of the sodium salt of the metal complex of formula Q20 there is used the same amount of the product of formula

The absorption maximum of a recording support analogous to Example 7 is at about 630 nm.

EXAMPLES 2465-2470

Analogously to Example 7, recording supports are produced using the products of other Examples. The following absorption maxima are obtained:

Recording support comprising product according to Example Example: Absorption maximum 2465  98 623 nm 2466  183 636 nm 2467 1227 632 nm 2468 1576 621 nm 2469 1583 625 nm 2470 1921 633 nm 

1. An optical recording medium, comprising a substrate and a recording layer, wherein the recording layer comprises a compound of formula (I)

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ are each independently of the others hydrogen, G₁, or C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, C₃-C₂₄cycloalkyl, C₃-C₂₄cycloalkenyl, C₇-C₂₄aralkyl, C₆-C₂₄aryl, C₄-C₁₂heteroaryl or C₁-C₁₂heterocycloalkyl, each unsubstituted or substituted by one or more identical or different substituents G₁, wherein R₁ and R₂, R₁ and R₁₃, R₂ and R₃, R₃ and R₄, R₄ and R₅, R₅ and R₆, R₆ and R₇, R₇ and R₈, R₈ and R₉, R₉ and R₁₀, R₁₀ and R₁₁, R₁₁ and R₁₂ and/or R₁₂ and R₁₃ can independently of one another be bonded to one another in pairs separately or, when they contain substitutable sites, via a direct bond or via a —CH₂—, —O—, —S—, —NH— or —NC₁-C₂₄alkyl-bridge in such a manner that, together with the atoms and bonds indicated in formula (I), five- or six-membered, saturated, unsaturated or aromatic, unsubstituted or G₁-substituted rings are formed, G₁ is any desired substituent, X^(m−) is an inorganic, organic or organometallic anion, Y^(n+) is a proton or a metal, ammonium or phosphonium cation, and m and n are each independently of the other a number from 1 to 5, and p and q are each independently of the other 0 or a number from 0.2 to 6, the ratio of p and q to one another, depending upon m and n and, as applicable, the number of charged G₁, being such that in formula (I) there is no excess positive or negative charge.
 2. A recording medium according to claim 1, which additionally comprises a reflecting layer.
 3. A recording medium according to claim 1, wherein R₆ is

and R₂₉, R₃₀ and R₃₁ are each independently of the others hydrogen, halogen, COOR₃₂, OR₃₂ or NR₃₂R₃₃, wherein R₃₂ and R₃₃ are each independently of the other hydrogen or C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₁-C₁₂cycloalkyl, C₂-C₁₂cycloalkenyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl, each unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical and uninterrupted or interrupted by 1, 2, 3, 4 or 5 oxygen and/or silicon atoms.
 4. A recording medium according to claim 1, wherein R₁, R₄, R₅, R₇, R₈ and R₁₁ are hydrogen; R₂, R₃, R₉, R₁₀, R₁₂ and R₁₃ are each independently of the others methyl, ethyl or R₁₄, it being possible for R₂ and R₃, R₉ and R₁₀, R₁₂ and R₁₃ and/or R₉ and R₁₀ also to be bonded together in pairs via a direct bond, methylene, —O— or —N(C₁-C₄alkyl); and R₆ is hydrogen or C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl, each unsubstituted or mono- to tetra-substituted by halogen, —O⁻, —OR₂₆, —CN, —NR₂₆R₂₇, —N⁺R₂₆R₂₇R₂₈, —N(R₂₆)COR₂₇, —COO⁻, —COOR₂₆, —CONR₂₆R₂₇, R₁₄ or by —N(R₂₆)COR₂₇R₂₈, wherein R₂₆, R₂₇ and R₂₈ are each independently of the others C₁-C₁₂alkyl, C₆-C₁₂aryl or C₇-C₁₃aralkyl.
 5. A recording medium according to claim 3, wherein R₆ is

or R₃₇, and R₃₄, R₃₅ and R₃₆ are each independently of the others hydrogen or R₃₇, R₃₇ being alkyl uninterrupted or interrupted by from 1 to 3 oxygen and/or silicon atoms and unsubstituted or substituted by one or two hydroxy substituents or by a metallocenyl or azo metal complex radical.
 6. A recording medium according to claim 1, wherein X^(m−) is a metal complex of formula [(L₁)M₁(L₂)]^(m−) (III) or [(L₃)M₂(L₄)]⁻ (IV), wherein M₁ and M₂ are a transition metal, m is a number from 1 to 6, L₁ and L₂ are each independently of the other a ligand of the formula

and L₃ and L₄ are each independently of the other a ligand of formula

wherein R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ are each independently of the others hydrogen, halogen, cyano, R₂₄, NO₂, NR₂₄R₂₅, NHCO—R₂₄, NHCOOR₂₄, SO₂—R₂₄, SO₂NH₂, SO₂NHR₂₄, SO₂NR₂₄R₂₅, SO₃ ⁻ or SO₃H, and R₂₂ and R₂₃ are each independently of the others CN, CONH₂, CONHR₂₄, CONR₂₄R₂₅, COOR₂₄ or COR₂₄, wherein R₂₄ and R₂₅ are each independently of the other C₁-C₁₂alkyl, C₁-C₁₂alkoxy-C₂-C₁₂alkyl, C₇-C₁₂aralkyl or C₆-C₁₂aryl, each unsubstituted or substituted by hydroxy, halogen, sulfato, C₁-C₆alkoxy, C₁-C₆alkylthio, C₁-C₆alkylamino or by di-C₁-C₆alkylamino, or R₂₄ and R₂₅ together are C₄-C₁₀heterocycloalkyl; it also being possible for R₁₆ and R₁₇, R₁₈ and R₁₉, and/or R₂₀ and R₂₁ to be bonded together in pairs in such a manner that a 5- or 6-membered ring is formed.
 7. A recording medium according to claim 1, wherein Y^(n+) is [NH₂R₃₈R₃₉]⁺, R₃₈ being hydrogen or C₁-C₁₂alkyl and R₃₉ being C₁-C₂₄alkyl or C₇-C₂₄aralkyl, and R₃₈ and R₃₉ together having from 8 to 25 carbon atoms.
 8. A recording medium according to claim 1, wherein m and n are each the number 1, p is a number from 1 to 2½, and q is a number from 0 to 1½, the sum of positive charges in formula (I) or (II) being equal to the sum of negative charges.
 9. A recording medium according to claim 1, wherein the dye of formula (I) has an absorption maximum at from 540 to 640 nm in ethanolic solution and a refractive index of from 2.0 to 3.0 in the range of from 600 to 700 nm in the solid.
 10. A recording medium according to claim 1, wherein the substrate has a transparency of at least 90% and a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm.
 11. A recording medium according to claim 2, wherein the reflecting layer consists of aluminium, silver, copper, gold or an alloy thereof and has a reflectivity of at least 45% and thickness of from 10 to 150 nm.
 12. A recording medium according to claim 2, wherein the recording layer is located between the transparent substrate and the reflecting layer and has a thickness of from 10 to 1000 nm.
 13. A recording medium according to claim 2, the uppermost layer of which is provided with an additional protective layer having a thickness of from 0.1 to 1000 μm to which there may be applied a second substrate layer that is from 0.1 to 5 mm thick and consists of the same material as the support substrate.
 14. A recording medium according to claim 1, which has a reflectivity of at least 15%.
 15. A recording medium according to claim 2, wherein between the recording layer and the reflecting layer and/or between the recording layer and the substrate there is additionally arranged at least one interference layer consisting of a dielectric material.
 16. A method for optical recording, storage and playback of information, which comprises the optical recording, storage and playback of the information from a recording medium according to claim
 1. 17. A method according to claim 16, wherein the recording and the playback take place in a wavelength range of from 600 to 700 nm.
 18. A process for the production of an optical recording medium, wherein a solution of a compound of formula (I) according claim 1 in an organic solvent is applied to a substrate having pits.
 19. A process according to claim 18, wherein the application is carried out by means of spin-coating.
 20. A compound of formula (I) according to claim
 1. 21. A process for the preparation of a compound of formula (I) according to claim 1, wherein a compound of structure

is oxidised in the presence of a C₁-C₁₈carboxylic acid.
 22. A process according to claim 21, wherein (meta)periodate is used as oxidising agent. 